Capped multi- or dual-headed compositions useful for chain shuttling and process to prepare the same

ABSTRACT

The present disclosure relates to a capped, multi- or dual-headed chain composition comprising derivatives of a strained olefin. The present disclosure further relates to a process for synthesizing the capped, multi- or dual-headed composition by using an organometallic compound and a co-catalyst in the presence of a catalyst precursor and a strained olefm. The present disclosure further relates to use of the compositions, as well as the process to make the same, in olefin polymerization.

FIELD

Embodiments relate to capped multi- or dual-headed compositions usefulfor chain shuttling and a process to prepare the same. In one aspect,the capped compositions can be used in olefin polymerization.

INTRODUCTION

The properties and applications of polyolefins depend to varying degreesupon the specific features of the catalysts used in their preparation.Specific catalyst compositions, activation conditions, steric andelectronic features, and the like all can factor into thecharacteristics of the resulting polymer product. Indeed, a multitude ofpolymer features, such as co-monomer incorporation, molecular weight,polydispersity, and long-chain branching, and the related physicalproperties, such as density, modulus, melt properties, tensile features,and optical properties, can all be affected by catalyst design.

In recent years, advances in polymer design have been seen with the useof compositions useful for chain shuttling. Such compositions havereversible chain transfer ability which can exchange a growing polymerchain between different catalytic sites such that portions of a singlepolymer molecule are synthesized by at least two different catalysts.These compositions also can extend the lifetime of a growing polymerchain such that sections of the polymer chain can be made in more thanone zone or reactor under different process conditions. Currently, thebest known compositions useful for chain shuttling are simple metalalkyls that typically contain only a single point of attachment to themetal for each polymer chain, such as diethyl zinc which producespolymer chains terminated with zinc metal at one end. More sophisticatedcompositions useful for chain shuttling, such as multi- or dual-headedchain shuttling agents (CSAs), with the alkane moiety attached to twometals, are also known. Indeed, multi- or dual-headed CSAs are of greatinterest since they can enable the production of new polyolefins, suchas telechelic functional polymers. However, significant challenges existfor use of multi- or dual-headed CSAs to produce high purity telechelicpolymer chains in reactors.

SUMMARY

In certain embodiments, the present disclosure relates to a compositionhaving the formula (I):

or an aggregate thereof, a Lewis base-containing derivative thereof, orany combination thereof, wherein:

each MA is Al, B, or Ga;

each MB is Zn or Mg;

m is a number from 0 to 1;

n is a number from 1 to 100;

YY is a derivative of a linking group, wherein the linking group is aC₄₋₁₀₀ hydrocarbon comprising at least two vinyl groups and optionallyincludes at least one heteroatom; and

each J2 and J3 is a derivative of a strained olefin.

In certain embodiments, the present disclosure relates to a process forpreparing the composition having the formula (I) comprising: (a)combining a linking group, an organometallic compound, a co-catalyst, asolvent, a first catalyst precursor, and a strained olefin, and (b)obtaining a final solution comprising the composition having the formula(I), wherein the linking group is a C₄₋₁₀₀ hydrocarbon comprising atleast two vinyl groups and optionally includes at least one heteroatom.

In certain embodiments, the present disclosure relates to apolymerization process for preparing a polymer composition, the processcomprising: contacting at least one olefin monomer with a catalystcomposition, wherein the catalyst composition comprises the reactionproduct of a second catalyst precursor, a co-catalyst, and thecomposition having the formula (I).

In certain embodiments, the present disclosure relates to apolymerization process for preparing a polymer composition, the processcomprising: contacting at least one olefin monomer with a catalystcomposition; wherein the catalyst composition comprises the reactionproduct of a second catalyst precursor, a co-catalyst, and thecomposition having the formula (I), and wherein the second catalystprecursor may be the same compound as the first catalyst precursor usedfor preparing the composition having the formula (I).

In certain embodiments, the present disclosure relates to a catalystcomposition comprising the reaction product of at least one catalystprecursor, at least one co-catalyst, and the composition having theformula (I).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 provides the ¹H NMR spectra of the composition of the ReferenceExample.

FIG. 2 provides the ¹³C NMR spectra of the composition of the ReferenceExample.

FIGS. 3A and 3B provide the GCMS of the composition of the ReferenceExample.

FIG. 4 provides the ¹³C NMR spectra of deuterium labeled polyethylenepolymerized in the presence of the composition of the Reference Example.

FIG. 5 provides the ¹H NMR spectra of the composition of Working Example1.

FIGS. 6 and 7 provide the GCMS of the composition of Working Example 1.

FIG. 8 provides the ¹³C NMR spectra of deuterium labeled polyethylenepolymerized in the presence of the composition of Working Example 1.

FIG. 9 provides the GPC curve of polyethylene polymerized in thepresence of the composition of Working Example 1.

FIG. 10 provides the ¹H NMR spectra of the composition of WorkingExample 2.

FIG. 11 provides the GCMS of the composition of Working Example 2.

FIG. 12 provides the GCMS of the composition of Working Example 3.

FIG. 13 provides the ¹H NMR spectra of the composition of WorkingExample 4.

FIG. 14 provides the GCMS of the composition of Working Example 4.

FIG. 15 provides the ¹³C NMR spectra of deuterium labeled polyethylenepolymerized in the presence of the composition of Working Example 4.

FIG. 16 provides the GPC curve of polyethylene polymerized in thepresence of the composition of Working Example 4.

FIG. 17 provides the GCMS of the composition of Working Example 5 beforesilica treatment.

FIG. 18 provides the GCMS of the composition of Working Example 5 aftersilica treatment.

FIG. 19 provides the ¹³C NMR spectra of the polymer produced with regardto Working Example 6.

FIG. 20 provide the TGIC curve of the polymer produced with regard toWorking Example 6.

DETAILED DESCRIPTION

Embodiments of the present disclosure relate to a capped multi- ordual-headed composition (i.e., the composition having the formula (I))as well as a process to prepare the same. In certain embodiments, thecomposition having the formula (I) may be a multi- or dual-headed chainshuttling agent. In further embodiments, the composition having theformula (I) may be a multi- or dual-headed chain transfer agent. Incertain embodiments, the composition having the formula (I) may becapable of producing a telechelic functional polymer.

Definitions

All references to the Periodic Table of the Elements refer to thePeriodic Table of the Elements published and copyrighted by CRC Press,Inc., 1990. Also, any references to a Group or Groups shall be to theGroup or Groups reflected in this Periodic Table of the Elements usingthe IUPAC system for numbering groups. Unless stated to the contrary,implicit from the context, or customary in the art, all parts andpercents are based on weight and all test methods are current as of thefiling date of this disclosure. For purposes of United States patentpractice, the contents of any referenced patent, patent application orpublication are incorporated by reference in their entirety (or itsequivalent U.S. version is so incorporated by reference in itsentirety), especially with respect to the disclosure of synthetictechniques, product and processing designs, polymers, catalysts,definitions (to the extent not inconsistent with any definitionsspecifically provided in this disclosure), and general knowledge in theart.

Number ranges in this disclosure and as they relate to the compositionhaving the formula (I) are approximate, and thus may include valuesoutside of the range unless otherwise indicated. Number ranges includeall values from and including the lower and the upper values, includingfractional numbers or decimals.

In the event the name of a compound herein does not conform to thestructural representation thereof, the structural representation shallcontrol.

With reference to the composition having the formula (I), as one ofordinary skill in the art would understand, should m be the number 1, J3and MA would be excluded from (and MB would be included in) thecomposition having the formula (I). Likewise, should m be the number 0,MB would be excluded from (and J3 and MA would be included in) thecomposition having the formula (I).

In certain embodiments, each of J1, J2, and J3 may be a hydrocarbylgroup. Examples of the hydrocarbyl group include C₁₋₂₀ alkyl groups(branched or unbranched), aryl groups, and aryl alkyl groups. Specificexamples of the hydrocarbyl group include but are not limited to methyl,ethyl, n-propyl, n-butyl, isobutyl, n-hexyl, isohexyl, n-octyl,isooctyl, or isomers thereof. In certain embodiments, the hydrocarbylgroup may be a substituted hydrocarbyl group with at least onesubstituent containing a heteroatom. Heteroatom as used herein includesall atoms with the exception of hydrogen and carbon.

The terms “chain shuttling agent” and “chain transfer agent” refer tothose known to one of ordinary skill in the art. Specifically, the term“shuttling agent” or “chain shuttling agent” refers to a compound ormixture of compounds that is capable of causing polymeryl transferbetween various active catalyst sites under conditions ofpolymerization. That is, transfer of a polymer fragment occurs both toand from an active catalyst site in a facile and reversible manner Incontrast to a shuttling agent or chain shuttling agent, an agent thatacts merely as a “chain transfer agent,” such as some main-group alkylcompounds, may exchange, for example, an alkyl group on the chaintransfer agent with the growing polymer chain on the catalyst, whichgenerally results in termination of the polymer chain growth. In thisevent, the main-group center may act as a repository for a dead polymerchain, rather than engaging in reversible transfer with a catalyst sitein the manner in which a chain shuttling agent does. Desirably, theintermediate formed between the chain shuttling agent and the polymerylchain is not sufficiently stable relative to exchange between thisintermediate and any other growing polymeryl chain, such that chaintermination is relatively rare.

“Multi- or dual-headed chain shuttling agents,” such as those disclosedin U.S. Pat. No. 8,501,885 B2 and those known in the art, includespecies with metal-alkyl bonds that engage in chain transfer during atransition-metal catalyzed polymerization. Because these chain shuttlingagents can be oligomeric, can consist of blends of species, or both, itis difficult to precisely describe these agents because, as they areused in solution, the CSA solution typically comprises a complex mixtureof different species. Therefore, the useful CSAs disclosed here aretypically described using average compositions, average numbers ofmulti-headed site valencies, average numbers of single-headed sitevalencies, and ratios of these numbers.

The terms “dual-headed” or “multi-headed” refer to a compound ormolecule containing more than one chain shuttling moiety joined by apolyvalent linking group. By way of illustration only, one example of adual-headed CSA is provided in the compounds of the general formulasR¹—[Zn—R²—]_(N)Zn—R¹ or R¹—[AlR¹—R²—]_(N)AlR¹ ₂, in which R¹ is amonovalent hydrocarbyl group and R² is a divalent hydrocarbadiyl group.In practice, suitable chain shuttling moieties typically include metalcenters derived from a metal selected from Groups 2-14 of the PeriodicTable of the Elements and having one or more available valencies capableof reversibly binding a growing polymer chain prepared by a coordinationpolymerization catalyst. At the same time that the chain shuttlingmoiety binds to the growing polymer chain, the remnant of the polyvalentlinking group remaining after loss of the chain shuttling moiety ormoieties incorporates or otherwise bonds to one or more active catalystsites, thereby forming a catalyst composition containing an activecoordination polymerization site capable of polymer insertion at oneterminus of what was originally the polyvalent linking group. Shuttlingof the new polymer chain attached to the linking group back to the chainshuttling moiety effectively grows a fraction of polymer chainscontaining a linking group and attached to a main group metal CSA atboth ends.

The term “derivative” used herein refers to the reaction product of achemical group after the insertion reaction of said chemical group intometal alkyl bonds. For example, the “R²” in R¹—[Zn—R²—]_(N)Zn—R¹ candefine the derivative reaction product of the linking groupCH₂═CH(CH₂)₆CH═CH₂ and Zn(Et)₂ to formEtZnRCH₂C(Et)H(CH₂)₆C(Et)HCH₂)Zn]_(N)Et. In this example, R² is—CH₂C(Et)H(CH₂)₆C(Et)HCH₂—, a derivative of the insertion of linkinggroup CH₂═CH(CH₂)₆CH═CH₂ into Zn—Et bonds.

The term “linking group” is a chemical species whose derivative linksmultiple metal species together in a molecule by inserting into a metalalkyl bond of each metal. In the above example, CH₂═CH(CH₂)₆CH═CH is a“linking group” which joins N+1 zinc species to form the speciesEtZn[(CH₂C(Et)H(CH₂)₆C(Et)HCH₂)Zn]_(N)Et.

As a further non-limiting example of the terms “derivative” and “linkinggroup” used herein, the “Y” in R—[Zn—Y—]_(n)Zn—R can define thederivative (i.e., reaction product) of the linking group1,2,4-trivinylcyclohexane (TVCH) to form the exemplary, non-limitingstructure shown below. In this example, Y is the structure sandwichedbetween zinc atoms; said structure is a derivative of the insertion oflinking group TVCH into Zn—R bonds.

The term “precursor” or “catalyst precursor” used herein refers to atransition metal species that, once combined with an activatorco-catalyst, is capable of polymerization of unsaturated monomers. Forexample, Cp₂Zr(CH₃)₂ is a catalyst precursor, which, when combined withan activating cocatalyst, becomes the active catalyst species“Cp₂Zr(CH₃)⁺” which is capable of polymerization of unsaturatedmonomers.

A “capping group” is a species that will insert into a primary metalalkyl bond essentially irreversibly such that the rate of further chaintransfer or chain shuttling reactions from this derivative is very low.

With reference to the composition having the formula (I) or anystructural formulae falling within the definition of formula (I), thesymbol “*” used herein refers to a carbon-metal bond serving as thepoint of attachment between the carbon of a substituent group and themetal (MA or MB) of the composition having the formula (I).

“Catalyst precursors” include those known in the art and those disclosedin WO 2005/090426, WO 2005/090427, WO 2007/035485, WO 2009/012215, WO2014/105411, U.S. Patent Publication Nos. 2006/0199930, 2007/0167578,2008/0311812, and U.S. Pat. Nos. 7,355,089 B2, 8,058,373 B2, and8,785,554 B2, all of which are incorporated herein by reference in theirentirety. The terms “transition metal catalysts,” “transition metalcatalyst precursors,” “catalysts,” “catalyst precursors,”“polymerization catalysts or catalyst precursors,” “procatalysts,”“metal complexes,” “complexes,” “metal-ligand complexes,” and like termsare to be interchangeable in the present disclosure.

“Organometallic compound” refers to any compound that contains ametal-carbon bond, R—M, and includes those known in the art as itrelates to the present disclosure.

“Co-catalyst” refers to those known in the art, e.g., those disclosed inWO 2005/090427 and U.S. Pat. No. 8,501,885 B2, that can activate thecatalyst precursor to form an active catalyst composition. “Activator”and like terms are used interchangeably with “co-catalyst.”

The term “catalyst system,” “active catalyst,” “activated catalyst,”“active catalyst composition,” “olefin polymerization catalyst,” andlike terms are interchangeable and refer to a catalystprecursor/co-catalyst pair. Such terms can also include more than onecatalyst precursor and/or more than one activator and optionally aco-activator. Likewise, these terms can also include more than oneactivated catalyst and one or more activator or other charge-balancingmoiety, and optionally a co-activator.

“Solvent” refers to those known in the art and those known asappropriate by one of ordinary skill in the art for the presentdisclosures. Suitable solvents include aromatic hydrocarbons, such astoluene, and aliphatic hydrocarbons, such as Isopar™ and heptane.

“Polymer” refers to a compound prepared by polymerizing monomers,whether of the same or a different type. The generic term polymer thusembraces the term homopolymer, usually employed to refer to polymersprepared from only one type of monomer, and the term interpolymer asdefined below. It also embraces all forms of interpolymers, e.g.,random, block, homogeneous, heterogeneous, etc.

“Interpolymer” and “copolymer” refer to a polymer prepared by thepolymerization of at least two different types of monomers. Thesegeneric terms include both classical copolymers, i.e., polymers preparedfrom two different types of monomers, and polymers prepared from morethan two different types of monomers, e.g., terpolymers, tetrapolymers,etc.

The term “block copolymer” or “segmented copolymer” refers to a polymercomprising two or more chemically distinct regions or segments (referredto as “blocks”) joined in a linear manner, that is, a polymer comprisingchemically differentiated units which are joined (covalently bonded)end-to-end with respect to polymerized functionality, rather than inpendent or grafted fashion. The blocks differ in the amount or type ofcomonomer incorporated therein, the density, the amount ofcrystallinity, the type of crystallinity (e.g., polyethylene versuspolypropylene), the crystallite size attributable to a polymer of suchcomposition, the type or degree of tacticity (isotactic orsyndiotactic), regio-regularity or regio-irregularity, the amount ofbranching, including long chain branching or hyper-branching, thehomogeneity, and/or any other chemical or physical property. The blockcopolymers are characterized by unique distributions of both polymerpolydispersity (PDI or Mw/Mn) and block length distribution, e.g., basedon the effect of the use of a shuttling agent(s) in combination withcatalysts.

Capped Multi- or Dual-Headed Compositions Having the Formula (I)

All schemes and discussions below are by way of example only and are notmeant to be limiting in any way. As noted herein, multi- or dual-headedcompositions (e.g., multi- or dual-headed CSAs) are of great interestsince they can enable production of telechelic functional polymers.Specifically, with reference to the generic dual-headed composition ofexemplary, non-limiting Scheme 1, the core YY group sandwiched betweentwo zinc atoms can grow into a polymer chain with both terminal ends ofthe chain bonded to the zinc atoms via terminal polymeryl-metal bonds.Subsequently, the terminal polymeryl-metal bonds may be transformed todesired functional groups via functionalization chemistry, therebyresulting in a desired di-functional polymer chain. The composition ofexemplary, non-limiting Scheme 1 may be in monomeric (n=1) or oligomeric(n>1) forms. In this case, zinc is an exemplary, non-limiting metal. Inthis case, YY may be a derivative of a linking group, where the linkinggroup is a C₄₋₁₀₀ hydrocarbon comprising at least two vinyl groups andoptionally includes at least one heteroatom.

However, significant challenges exist for producing high-puritytelechelic polymers in reactors. For example, as seen in exemplary,non-limiting Scheme 1, the zinc atoms at the terminal ends of anoligomeric, dual-headed composition bear pendant/terminal R′ groups. Inthis case, the pendant R′ groups may be alkyl groups, which may be morereactive for chain transfer reactions than the core YY group moiety inthe middle of the composition. Thus, during polymerization, the terminalR′ groups will grow into polymer chains that become unwantedmono-functional polymer chains after functionalization. One way toreduce the amount of unwanted mono-functional polymer chains relative tothe desired di-functional polymer chains is to increase the (n) value ofthe oligomer; however, such an approach will result in higher in-reactormolecular weight chains which will cause reactor operability issues(e.g., high viscosity), especially for solution processes. Accordingly,there is a critical need in the state of the art for a way to preventthe terminal R′ groups from growing into unwanted mono-functionalpolymers in order to produce, from the core YY group, di-functionalpolymers with acceptable purity.

In certain embodiments, the present disclosure relates, for example, toreplacing the terminal R′ groups of exemplary, non-limiting Scheme 1with capping groups that have very low rates of chain transfer or chainshuttling with the polymerization catalyst, and will therefore not growinto polymer chains (i.e., no unwanted mono-functional polymer chainswill be produced). As a result, only desired di-functional polymerchains will grow from the core YY group via olefin polymerization andfunctionalization, thereby enabling production of pure telechelicpolymers.

Accordingly, in certain embodiments, the present disclosure relates to amulti- or dual-headed composition having terminal capping groups, asseen in the composition having the formula (I) with regard to J2 and J3,which are each a derivative of a strained olefin.

Additionally, certain embodiments of the present disclosure relate to aprocess for preparing the composition having the formula (I) comprising:(a) combining a linking group, an organometallic compound, aco-catalyst, a solvent, a catalyst precursor, and a strained olefin, and(b) obtaining a final solution comprising the composition having theformula (I), wherein the linking group is a C₄₋₁₀₀ hydrocarboncomprising at least two vinyl groups and optionally includes at leastone heteroatom. In this case, the terminal capping groups of thecomposition having the formula (I) prepared by this process will be J2and J3, which are each a derivative of the strained olefin.

In further embodiments, the process for preparing the composition havingthe formula (I) comprises: (a) combining a linking group, anorganometallic compound, a co-catalyst, a solvent, and a catalystprecursor to form a first solution; and (b) combining the first solutionwith a strained olefin to form a final solution comprising thecomposition having the formula (I), wherein the linking group is aC₄₋₁₀₀ hydrocarbon comprising at least two vinyl groups and optionallyincludes at least one heteroatom. In this regard, additionalorganometallic compound and co-catalyst may optionally be added during(b).

In certain embodiments, the process for preparing the composition havingthe formula (I) is a one-pot process without any isolation,purification, or separation requirements. In further embodiments, theprocess for preparing the composition having the formula (I) is aone-pot process; the catalyst precursor (in combination with theco-catalyst) remains as an active catalyst in the final solution, canfurther function as an active catalyst for subsequent olefinpolymerization, and need not be removed prior to subsequent olefinpolymerization. In certain embodiments, the catalyst precursor has nodetrimental effect on subsequent olefin polymerization and is a goodhigher alpha-olefin incorporating (i.e., good comonomer incorporating)catalyst.

In certain embodiments, the composition having the formula (I) remainsactive in the final solution and can further function as a chainshuttling agent or chain transfer agent during olefin polymerization.Thus, in certain embodiments, the process of the present disclosure is aone-pot process, and the final solution of the process (containing theactive catalyst and the composition having the formula (I)) can bedirectly used in olefin polymerization reactions without any isolation,purification, or separation requirements and without the requirement ofhaving a removable supported catalyst.

Accordingly, in certain embodiments, the present disclosure relates to apolymerization process for the polymerization of at least one additionpolymerizable monomer (i.e., olefin monomer) to form a polymercomposition, the process comprising: contacting at least one additionpolymerizable monomer (i.e., olefin monomer) with a catalyst compositionunder polymerization conditions; wherein the catalyst compositioncomprises the contact product (i.e., reaction product) of at least onecatalyst precursor, at least one co-catalyst, and the composition havingthe formula (I). In further embodiments, the present disclosure relatesto a polymerization process for the polymerization of at least oneaddition polymerizable monomer (i.e., olefin monomer) to form a polymercomposition, the process comprising: contacting at least one additionpolymerizable monomer (i.e., olefin monomer) with a catalyst compositionunder polymerization conditions; wherein the catalyst compositioncomprises the contact product (i.e., reaction product) of at least onecatalyst precursor, at least one co-catalyst, and the composition havingthe formula (I), and wherein the catalyst precursor for thepolymerization process is also the catalyst precursor used for preparingthe composition having the formula (I). In other words, the catalystprecursor used to form the composition having the formula (I) is thesame compound as the catalyst precursor used for olefin polymerizationreactions.

While the catalyst remaining in the final solution can be directly usedfor polymerization, in certain embodiments, the catalyst in the finalsolution may optionally be removed from the final solution prior topolymerization by means known to those of ordinary skill in the art,such as passing the final solution through a plug of silica, alumina, orother bed media that will remove the active catalyst without reactionwith or removal of more than a small percentage of the compositionhaving the formula (I). Preferably, the removal process uses dehydratedamorphous silica.

Strained Olefin Capping Groups

The terminal capping groups of the composition having the formula (I)may be selected from “strained olefins,” which include alkenes that formsterically hindered metal-carbon bonds. The chain transfer on thesesterically hindered sites are kinetically disfavored in competition withthe less hindered bonds between metal and the core YY group (i.e., thederivative of a linking group). Accordingly, unwanted mono-functionalpolymer chains are prevented from growing, as the capping groups makethe chain transfer reaction and polymer growth occur selectively on theless-hindered, core YY group of the composition having the formula (I).

Accordingly, in certain embodiments, the present disclosure relates toadding a strained olefin to cap the terminal ends of a multi- ordual-headed composition, as seen in Scheme 2, which is exemplary andnon-limiting:

The catalytic process for exemplary, non-limiting Scheme 2 is furtherdetailed in Scheme 3, which is also exemplary and non-limiting.

In certain embodiments, the capping groups are selected from “strainedolefins,” which include but are not limited to the following structuralformulae:

wherein:

each XX2, XX3, XX4, and XX5 is hydrogen, a substituted or unsubstitutedC₁₋₂₀ alkyl group, or a substituted or unsubstituted C₆₋₂₀ aryl group,

wherein XX2, XX3, XX4, and XX5 may be the same or different,

wherein each XX2, XX3, XX4, and XX5 optionally includes at least oneheteroatom, and

wherein two of XX2, XX3, XX4, and XX5 may optionally form cyclic ringsor cyclic structures.

In further embodiments, the capping groups are selected from strainedolefins, which include but are not limited to the following structuralformulae:

Accordingly, in certain embodiments, the composition having the formula(I) comprises capping groups as seen in formula (I) with regard to J2and J3, which are derivatives of strained olefins in accordance with thefollowing structural formulae:

wherein:

J1 is hydrogen or a C₁₋₂₀ alkyl group; and

each XX2, XX3, XX4, and XX5 is hydrogen, a substituted or unsubstitutedC₁₋₂₀ alkyl group, or a substituted or unsubstituted C₆₋₂₀ aryl group,

wherein XX2, XX3, XX4, and XX5 may be the same or different,

wherein each XX2, XX3, XX4, and XX5 optionally includes at least oneheteroatom, and

wherein two of XX2, XX3, XX4, and XX5 may optionally form cyclic ringsor structures.

In further embodiments, the composition having the formula (I) comprisescapping groups as seen in formula (I) with regard to J2 and J3, whichare derivatives of strained olefins in accordance with the followingstructural formulae:

wherein J1 is hydrogen or a C₁₋₂₀ alkyl group.

In certain embodiments, J1 of the structural formulae of the cappinggroups of the composition having the formula (I) may be methyl, ethyl,n-propyl, n-butyl, isobutyl, n-hexyl, isohexyl, n-octyl, or isooctyl.

Core Structure

With reference to the composition having the formula (I), the core YYgroup (i.e., the derivative of a linking group), during olefinpolymerization, will grow into polymer chains with both ends attached tothe metal atoms to enable production of telechelic polymers. In certainembodiments, YY is a derivative of a C₄₋₁₀₀ linking group comprising atleast two vinyl groups and optionally includes at least one heteroatom.In the case where YY is a derivative of a C4 linking group, two vinylgroups will be directly bound to each other.

In certain embodiments of the present disclosure, YY is a derivative ofa 1,2,4-trivinylcyclohexane (TVCH) linking group. Specifically, incertain embodiments, the compositions having the formula (I) formed withTVCH are formed via the exemplary, non-limiting mechanism illustratedbelow in Scheme 4 (which does not include insertion of the cappinggroups). With reference to exemplary, non-limiting Scheme 4, the vinyldouble bond on the top and one of the vinyl groups on the bottom of theTVCH ring coordinate with the catalyst precursor and insert into themetal-carbon bond to form (1). The remaining neighboring vinyl insertsto form (2), a 5-member ring, which then transfers to metal to form adual-headed metal species (3). The recovered metal catalyst precursorgoes back to the catalyst cycle to react with another TVCH molecule. Thedual headed metal species (3) undergoes further chain transfer with (2)using the remaining terminal ZnR2, resulting in “polymeric” dual headedmetal species. This catalyst process continues until TVCH is exhausted.The length of the dual headed zinc chain is primarily determined by themetal/TVCH ratio. The closer the ratio to unity, the greater is the nvalue.

Accordingly, in certain embodiments, the composition having the formula(I) has the following structural formulae with a YY core group being aderivative of a TVCH linking group:

or aggregates thereof, Lewis base-containing derivatives thereof, or anycombination thereof, wherein J1 is hydrogen or a C₁₋₂₀ alkyl group. Infurther embodiments, J1 of the derivative of TVCH may be methyl, ethyl,n-propyl, n-butyl, isobutyl, n-hexyl, isohexyl, n-octyl, or isooctyl.

In certain embodiments, YY of the composition having the formula (I) hasthe following structural formula:

wherein:

J1 is hydrogen or a C₁₋₂₀ alkyl group; and

ZZ is a linear or branched C₄₋₁₀₀ hydrocarbyl group that optionallyincludes at

least one heteroatom, and wherein ZZ may be aliphatic or aromatic.

In further embodiments of the immediately preceding structural formula,J1 may be methyl, ethyl, n-propyl, n-butyl, isobutyl, n-hexyl, isohexyl,n-octyl, or isooctyl.

In further embodiments of the immediately preceding structural formula,YY is a derivative of a diene, such as an alpha,omega diene (α,ω-diene).In certain embodiments, dienes suitable for the present disclosure mustbe able to coordinate with the catalyst precursor and insert into themetal-carbon bond to form δ-bond with the metal, then immediatelytransfer to the MA or MB metal (of the organometallic compound) of thepresent disclosure. In certain embodiments of the present disclosure,the consecutive insertion of a second diene is kinetically disfavoredbecause the rate of olefin insertion is much slower than the rate ofchain transfer to MA or MB metal (of the organometallic compound),resulting in only one diene molecule sandwiched between two MA or MBmetals.

As used here, the term “α,ω-diene” is used interchangeably with“α,ω-diene-containing” molecules or species to refer to any compoundthat contains at least two terminal olefin moieties (—CH═CH₂), and arenot intended to be limiting to strictly hydrocarbon species. Examples ofsuitable a,w-diene-containing species include hydrocarbyl α,ω-dienes,functionalized hydrocarbyl α,ω-dienes, such as heteroatom-functionalizeddiene compounds, and other a,w-diene-containing compounds, such as1,3-di(ω-alkenyl)-tetramethyldisiloxanes and di(ω-alkenyl)ethers.

Suitable hydrocarbyl α,ω-dienes as referred to herein include α,ω-dieneshaving the formula CH₂═CH(CH₂)_(n)CH═CH₂, where n is an integer from 0to 20, preferably n is an integer from 1 to 20, including cyclic andbicyclic analogs thereof. Examples of these hydrocarbyl α,ω-dienesinclude but are not limited to 1,3-butadiene, 1,4-pentadiene,1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene,1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, vinyl norbornene, norbornadiene, dicyclopentadiene,cyclooctadiene, vinyl cyclohexene, and the like, typically containingfrom 5 to 40 carbon atoms.

Functionalized hydrocarbyl α,ω-dienes as referred to herein includeα,ω-dienes which are heteroatom-substituted by at least one O, S, N, orSi atom, or a combination of atoms. Specific examples of functionalizedhydrocarbyl α,ω-dienes include but are not limited to compounds havingthe formulas O[(CH₂)_(n)CH═CH₂]₂, S[(CH₂)_(n)CH═CH₂]₂,R^(A)N[(CH₂)_(n)CH═CH₂]₂, (R^(B))₂Si[(CH₂)_(n)CH═CH₂]₂,(R^(B))₃SiOSiR^(B)[(CH₂)_(n)CH═CH₂]₂, and [Si(R^(B))₂(CH₂)_(n)CH═CH₂]₂O;wherein n in each occurrence is independently an integer from 0 to 20,inclusive, preferably 1 to 20 inclusive; R^(A) is H or a hydrocarbylhaving from 1 to 12 carbon atoms, inclusive; and, R^(B) in eachoccurrence is independently a hydrocarbyl having from 1 to 12 carbonatoms, inclusive.

Examples of functionalized hydrocarbyl α,ω-dienes include but are notlimited to divinyl ether, di(2-propenyl)ether, di(3-butenyl)ether,di(4-pentenyl)ether, di(5-hexenyl)ether, divinyl amine,di(2-propenyl)amine, di(3-butenyl)amine, di(4-pentenyl) amine,di(5-hexenyl)amine, divinyl methylamine, di(2-propenyl)methylamine,di(3-butenyl)methylamine, di(4-pentenyl)methylamine,di(5-hexenyl)methylamine, divinyl thioether, di(2-propenyl)thioether),di(3-butenyl)thioether, di(4-pentenyl)thioether, di(5-hexenyl)thioether,divinyl dimethylsilane, di(2-propenyl) dimethylsilane, di(3-butenyl)dimethylsilane, di(4-pentenyl) dimethylsilane, di(5-hexenyl)dimethylsilane, and the like, typically containing from 4 to 40 carbonatoms.

Further examples of suitable functionalized hydrocarbyl a,w-dienesinclude but are not limited to the disiloxane compounds, such as the1,1- and the 1,3-isomers of divinyl tetramethyldisiloxane (also referredto here as di(ethan-1,2-diyl) tetramethyldisiloxane),di(2-propenyl)tetramethyldisiloxane, di(3-butenyl)tetramethyldisiloxane,di(4-pentenyl)tetramethyldisiloxane, di(5-hexenyl)tetramethyldisiloxane,di(6-heptenyl)tetramethyldisiloxane, di(7-octenyl)tetramethyldisiloxane,di(8-nonenyl)tetramethyldisiloxane, di(9-decenyl)-tetramethyldisiloxane,divinyltetraethyldisiloxane, di(2-propenyl)tetraethyldisiloxane,di(3-butenyl)tetraethyldisiloxane, di(4-pentenyl)tetraethyldisiloxane,di(5-hexenyl)-tetraethyldisiloxane, di(6-heptenyl)tetraethyldisiloxane,di(7-octenyl)tetraethyldisiloxane, di(8-nonenyl)tetraethyldisiloxane,di(9-decenyl)tetraethyldisiloxane, and the like.

Specific examples of the diene compound include conjugated dienecompounds such as 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene,1,3-heptadiene, 1,3-octadiene, 1-phenyl-1,3-butadiene,1-phenyl-2,4-pentadiene, isoprene, 2-ethyl-1,3-butadiene,2-propyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-pentyl-1,3-butadiene,2-hexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-octyl-1,3-butadiene,and 2-phenyl-1,3-butadiene; chain non-conjugated diene compounds such as1,4-pentadiene, 3-methyl-1,4-pentadiene, 1,4-hexadiene,3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene,4,5-dimethyl-1,4-hexadiene, 1,5-hexadiene, 3-methyl-1,5-hexadiene,1,5-heptadiene, 3-methyl-1,5-heptadiene, 1,6-heptadiene,4-methyl-1,6-heptadiene, 1,6-octadiene, 4-methyl-1,6-octadiene,7-methyl-1,6-octadiene, 1,7-octadiene, 4-methyl-1,7-octadiene,1,7-nonadiene, 4-methyl-1,7-nonadiene, 1,8-nonadiene,4-methyl-1,8-nonadiene, 1,8-decadiene, 5-methyl-1,8-decadiene,1,9-decadiene, 5-methyl-1,9-decadiene, 1,10-undecadiene, and1,11-dodecadiene;

triene compounds such as 1,4,7-octatriene, 3-methyl-1,4,7-octatriene,1,5,9-decatriene, and 4-methyl-1,5,9-decatriene;

cyclic olefin compounds such as 5-methylene-2-norbornene,5-vinyl-2-norbornene, 5-(2-propenyl)-2-norbornene,5-(3-butenyl)-2-norbornene, 5-(1-methyl-2-propenyl)-2-norbornene,5-(4-pentenyl)-2-norbornene, 5-(1-methyl-3-butenyl)-2-norbornene,5-(5-hexenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene,5-(2,3-dimethyl-3-butenyl)-2-norbornene,5-(2-ethyl-3-butenyl)-2-norbornene, 5-(6-heptenyl)-2-norbornene,5-(3-methyl-5-hexenyl)-2-norbornene,5-(3,4-dimethyl-4-pentenyl)-2-norbornene,5-(3-ethyl-4-pentenyl)-2-norbornene, 5-(7-octenyl)-2-norbornene,5-(2-methyl-6-heptenyl)-2-norbornene,5-(1,2-dimethyl-5-hexenyl)-2-norbornene,5-(5-ethyl-5-hexenyl)-2-norbornene,5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene, dicyclopentadiene,5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene,1,1′-bi(3-cyclopentene), di(3-cyclopentenyl)methane,1,3-di(3-cyclopentenyl)propane, 1,4-di(3-cyclopentenyl)butane,1,5-di(3-cyclopentenyl)pentane, 3-methyl-1,1′-bi(3-cyclopentene),4-(3-cyclopentenylmethyl)-1 ethyl-1-cyclopentene,4-(3-(3-cyclopentenyl)propyl)-1-methyl-l-cyclopentene,4-(4-(3-cyclopentenyl)butyl)-1-methyl-1-cyclopentene,1,1′-bi(3-cyclohexene), di(3-cyclohexenyl)methane,1,3-di(3-cyclohexenyl)propane, 1,4-di(3-cyclohexenyl)butane, and1,5-di(3-cyclohexenyl)pentane;

cyclic diene compounds such as6-chloromethyl-5-isopropenyl-2-norbornene;

halogen-containing diene compounds such as 3-chloro-1,4-pentadiene,3-bromo-3-methyl-1,4-pentadiene, 3-chloro-1,4-hexadiene,3-chloro-3-methyl-1,4-hexadiene, 3-bromo-4-methyl-1,4-hexadiene,3-chloro-5-methyl-1,4-hexadiene, 3-bromo-4,5-dimethyl-1,4-hexadiene,3-bromo-1,5-hexadiene, 3-chloro-3-methyl-1,5-hexadiene,3-bromo-1,5-heptadiene, 3-chloro-3-methyl-1,5-heptadiene,4-bromo-1,6-heptadiene, 3-chloro-4-methyl-1,6-heptadiene,4-bromo-1,6-octadiene, 3-chloro-4-methyl-1,6-octadiene,4-bromo-7-methyl-1,6-octadiene, 4-chloro-1,7-octadiene,3-chloro-4-methyl-1,7-octadiene, 4-bromo-1,7-nonadiene,4-bromo-4-methyl-1,7-nonadiene, 4-bromo-1,8-nonadiene, 3-chloro-4-methyl1,8-nonadiene, 5-bromo-1,8-decadiene, 3-chloro-5-methyl-1,8-decadiene,5-bromo-1,9-decadiene, 3-chloro-5-methyl-1,9-decadiene,5-bromo-1,10-undecadiene, and 5-bromo-1,1′-dodecadiene;

silane-containing dienes such as bisvinyloxy silane, dimethylbisvinyloxy silane, bisallyloxy silane, dimethylbis allyloxy silane,di(3-butenyl)dimethyl silane, bis(3-butenyloxy)silane,dimethylbis(3-butenyloxy)silane, di(4-pentenyl)dimethyl silane,bis(4-pentenyloxy)silane, bis(4-pentenyloxy)dimethylsilane,di(5-hexenyl)dimethylsilane, bis(5-hexenyloxy)silane, andbis(5-hexenyloxy)dimethylsilane;

ester-containing diene compounds such as 3-butenyl-4-pentenoate,4-pentenyl-4-pentenoate, 4-methoxycarbonyl-1,7-octadiene, and4-methoxycarbonyl-1,9-decadiene;

ether-containing diene compounds such as divinyl ether, diallyl ether,di(4-butenyloxy)ether, and di(5-hexenyloxy)ether;

siloxy-containing diene compounds such as 4-trimethylsiloxymethyl-1,7-octadiene, and 4-trimethyl siloxymethyl-1,9-decadiene.

These diene compounds are generally available or can be produced byknown methods.

Organometallic Compound

In certain embodiments of the process of the present disclosure, theorganometallic compound is a metal alkyl. In certain embodiments of theprocess of the present disclosure, the organometallic compound is ametal alkyl containing a divalent metal (e.g., Zn or Mg), a trivalentmetal (e.g., Al, B, or Ga), or a mixture of divalent metal and trivalentmetal. In certain embodiments of the process of the present disclosure,the organometallic compound is a divalent metal alkyl, such asdialkylzinc. In certain embodiments of the process of the presentdisclosure, the organometallic compound is a trivalent metal alkyl, suchas trialkylaluminum. In certain embodiments of the process of thepresent disclosure, the organometallic compound is a mixture of divalentmetal alkyl (e.g., dialkylzinc) and trivalent metal alkyl (e.g.,trialkylaluminum).

Exemplary divalent metals suitable for the organometallic compound ofthe present disclosure include but are not limited to dimethyl zinc,diethyl zinc, dipropyl zinc, dibutyl zinc, diisobutyl zinc, dihexylzinc, diisohexyl zinc, dioctyl zinc, and diisooctyl zinc. Exemplarydivalent metals suitable for the organometallic compound of the presentdisclosure further include but are not limited to organomagnesiumcompounds, such as dimethyl magnesium, diethyl magnesium, dipropylmagnesium, dibutyl magnesium, diisobutyl magnesium, dihexyl magnesium,diisohexyl magnesium, dioctyl magnesium, and diisooctyl magnesium.

Exemplary trivalent metals suitable for the organometallic compound ofthe present disclosure include but are not limited to trimethylaluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum,triisobutyl aluminum, trihexyl aluminum, triisohexyl aluminum, trioctylaluminum, triisooctyl aluminum, tripentyl aluminum, tridecyl aluminum,tribranched alkyl aluminums, tricycloalkyl aluminums, triphenylaluminum, tritolyl aluminum, dialkyl and aluminum hydrides. Furthertrivalent metals include but are not limited to organogallium compounds,such as trimethyl gallium, triethyl gallium, tripropyl gallium, tributylgallium, triisobutyl gallium, trihexyl gallium, triisohexyl gallium,trioctyl gallium, and triisooctyl gallium.

In certain embodiments, J1, J2, and J3 of any and all of the structuralformulae discussed herein as they relate to the composition having theformula (I) may correspond to the alkyl group of the organometalliccompound of the process of the present disclosure.

In certain embodiments of the process of the present disclosure, theorganometallic compound, as it relates to “m” of formula (I), is a metalalkyl containing a mixture of trivalent metal and divalent metal at atrivalent metal/divalent metal ratio from 99:1 to 1:99 (e.g., from 95:5to 50:50, from 90:10 to 80:20, from 90:10 to 70:30, etc.). In certainembodiments of the process of the present disclosure, the organometalliccompound is a metal alkyl containing a mixture of aluminum and zincmetals at an aluminum/zinc ratio from 99:1 to 1:99 (e.g., from 95:5 to50:50, from 90:10 to 80:20, from 90:10 to 70:30, etc.).

In certain embodiments of the present disclosure, methods are consideredto control the formation of insoluble gel that can easily form due totrivalent metals. In certain embodiments of the process of the presentdisclosure, the formation of the insoluble gel with trivalent metals isprevented by controlling the ratio of metal to linking group, where thelinking group (i.e., the derivative of which becomes the YY group) is aC₄₋₁₀₀ hydrocarbon comprising at least two vinyl groups and optionallyincludes at least one heteroatom. The higher the metal/linking groupratio, the smaller the size of the oligomer and, thus, the lower thechance is for the formation of insoluble gel. In further embodiments,the structure and size of the composition of having the formula (I) maybe tailored as desired via selection of the organometallic compound andthe metal/linking group ratio. Indeed, the length (n) of the compositionhaving the formula (I) may be controlled by the metal/linking groupratio, where metal/linking group=(n+1)/n. Thus, for example, themetal/linking group ratio is 2 for n=1, the metal/linking group ratio is1.5 for n=2, the metal/linking group ratio is 1.33333 for n=3, etc. Atvery large “n” values, the metal/linking group ratio approaches 1.

In certain embodiments, the metal/linking group ratio is from 2:1 to 1:1(where the length (n) of the composition having the formula (I) is anumber from 1 to infinity). In further embodiments, the metal/linkinggroup ratio is from 3:2 to 11:10 (where the length (n) of thecomposition having the formula (I) is a number from 2 to 10).

Catalyst or Catalyst Precursor

Suitable catalyst precursors for use herein include any compound orcombination of compounds that is adapted for preparing polymers of thedesired composition or type and capable of reversible chain transferwith a chain shuttling agent. Both heterogeneous and homogeneouscatalysts may be employed. Examples of heterogeneous catalysts includethe well known Ziegler-Natta compositions, especially Group 4 metalhalides supported on Group 2 metal halides or mixed halides andalkoxides and the well known chromium or vanadium based catalysts.Preferably, the catalysts for use herein are homogeneous catalystscomprising a relatively pure organometallic compound or metal complex,especially compounds or complexes based on metals selected from Groups3-10 or the Lanthanide series of the Periodic Table of the Elements.

Metal complexes for use herein may be selected from Groups 3 to 15 ofthe Periodic Table of the Elements containing one or more delocalized,π-bonded ligands or polyvalent Lewis base ligands. Examples includemetallocene, half-metallocene, constrained geometry, and polyvalentpyridylamine, or other polychelating base complexes. The complexes aregenerically depicted by the formula: MK_(k)X_(x)Z_(z), or a dimerthereof, wherein

M is a metal selected from Groups 3-15, preferably 3-10, more preferably4-10, and most preferably Group 4 of the Periodic Table of the Elements;

K independently at each occurrence is a group containing delocalizedπ-electrons or one or more electron pairs through which K is bound to M,said K group containing up to 50 atoms not counting hydrogen atoms,optionally two or more K groups may be joined together forming a bridgedstructure, and further optionally one or more K groups may be bound toZ, to X or to both Z and X;

X independently at each occurrence is a monovalent, anionic moietyhaving up to 40 non-hydrogen atoms, optionally one or more X groups maybe bonded together thereby forming a divalent or polyvalent anionicgroup, and, further optionally, one or more X groups and one or more Zgroups may be bonded together thereby forming a moiety that is bothcovalently bound to M and coordinated thereto; or two X groups togetherform a divalent anionic ligand group of up to 40 non-hydrogen atoms ortogether are a conjugated diene having from 4 to 30 non-hydrogen atomsbound by means of delocalized n-electrons to M, whereupon M is in the +2formal oxidation state, and

Z independently at each occurrence is a neutral, Lewis base donor ligandof up to 50 non-hydrogen atoms containing at least one unshared electronpair through which Z is coordinated to M;

k is an integer from 0 to 3; x is an integer from 1 to 4; z is a numberfrom 0 to 3; and

the sum, k+x, is equal to the formal oxidation state of M.

Suitable metal complexes include those containing from 1 to 3 π-bondedanionic or neutral ligand groups, which may be cyclic or non-cyclicdelocalized π-bonded anionic ligand groups. Exemplary of such π-bondedgroups are conjugated or nonconjugated, cyclic or non-cyclic diene anddienyl groups, allyl groups, boratabenzene groups, phosphole, and arenegroups. By the term “π-bonded” is meant that the ligand group is bondedto the transition metal by a sharing of electrons from a partiallydelocalized π-bond.

Each atom in the delocalized π-bonded group may independently besubstituted with a radical selected from the group consisting ofhydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substitutedheteroatoms wherein the heteroatom is selected from Group 14-16 of thePeriodic Table of the Elements, and such hydrocarbyl-substitutedheteroatom radicals further substituted with a Group 15 or 16 heteroatom containing moiety. In addition two or more such radicals maytogether form a fused ring system, including partially or fullyhydrogenated fused ring systems, or they may form a metallocycle withthe metal. Included within the term “hydrocarbyl” are C₁₋₂₀ straight,branched and cyclic alkyl radicals, C₆₋₂₀ aromatic radicals, C₇₋₂₀alkyl-substituted aromatic radicals, and C₇₋₂₀ aryl-substituted alkylradicals. Suitable hydrocarbyl-substituted heteroatom radicals includemono-, di- and tri-substituted radicals of boron, silicon, germanium,nitrogen, phosphorus or oxygen wherein each of the hydrocarbyl groupscontains from 1 to 20 carbon atoms. Examples include N,N-dimethylamino,pyrrolidinyl, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl,methyldi(t-butyl)silyl, triphenylgermyl, and trimethylgermyl groups.Examples of Group 15 or 16 hetero atom containing moieties includeamino, phosphino, alkoxy, or alkylthio moieties or divalent derivativesthereof, for example, amide, phosphide, alkyleneoxy or alkylenethiogroups bonded to the transition metal or Lanthanide metal, and bonded tothe hydrocarbyl group, π-bonded group, or hydrocarbyl-substitutedheteroatom.

Examples of suitable anionic, delocalized π-bonded groups includecyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl,dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups,phosphole, and boratabenzyl groups, as well as inertly substitutedderivatives thereof, especially C₁₋₁₀ hydrocarbyl-substituted ortris(C₁₋₁₀ hydrocarbyl)silyl-substituted derivatives thereof. Preferredanionic delocalized π-bonded groups are cyclopentadienyl,pentamethylcyclopentadienyl, tetramethylcyclopentadienyl,tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl,fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl,tetrahydrofluorenyl, octahydrofluorenyl, 1-indacenyl,3-pyrrolidinoinden-1-yl, 3,4-(cyclopenta(l)phenanthren-1-yl, andtetrahydroindenyl.

The boratabenzenyl ligands are anionic ligands which are boroncontaining analogues to benzene. They are previously known in the arthaving been described by G. Herberich, et al., in Organometallics, 14,1,471-480 (1995). Preferred boratabenzenyl ligands correspond to theformula:

wherein R¹ is an inert substituent, preferably selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, halo or germyl, said R¹having up to 20 atoms not counting hydrogen, and optionally two adjacentIV groups may be joined together. In complexes involving divalentderivatives of such delocalized π-bonded groups one atom thereof isbonded by means of a covalent bond or a covalently bonded divalent groupto another atom of the complex thereby forming a bridged system.

Phospholes are anionic ligands that are phosphorus containing analoguesto a cyclopentadienyl group. They are previously known in the art havingbeen described by WO 98/50392, and elsewhere. Preferred phospholeligands correspond to the formula:

wherein R¹ is as previously defined.

Suitable transition metal complexes for use herein correspond to theformula: MK_(k)X_(x)Z_(z), or a dimer thereof, wherein:

M is a Group 4 metal;

K is a group containing delocalized π-electrons through which K is boundto M, said K group containing up to 50 atoms not counting hydrogenatoms, optionally two K groups may be joined together forming a bridgedstructure, and further optionally one K may be bound to X or Z;

X at each occurrence is a monovalent, anionic moiety having up to 40non-hydrogen atoms, optionally one or more X and one or more K groupsare bonded together to form a metallocycle, and further optionally oneor more X and one or more Z groups are bonded together thereby forming amoiety that is both covalently bound to M and coordinated thereto;

Z independently at each occurrence is a neutral, Lewis base donor ligandof up to 50 non-hydrogen atoms containing at least one unshared electronpair through which Z is coordinated to M;

k is an integer from 0 to 3; x is an integer from 1 to 4; z is a numberfrom 0 to 3; and the sum, k+x, is equal to the formal oxidation state ofM.

Suitable complexes include those containing either one or two K groups.The latter complexes include those containing a bridging group linkingthe two K groups. Suitable bridging groups are those corresponding tothe formula (ER′₂)_(e) wherein E is silicon, germanium, tin, or carbon,R′ independently at each occurrence is hydrogen or a group selected fromsilyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R′having up to 30 carbon or silicon atoms, and e is 1 to 8.Illustratively, R′ independently at each occurrence is methyl, ethyl,propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy or phenoxy.

Examples of the complexes containing two K groups are compoundscorresponding to the formula:

wherein:

M is titanium, zirconium or hafnium, preferably zirconium or hafnium, inthe +2 or +4 formal oxidation state; R³ at each occurrence independentlyis selected from the group consisting of hydrogen, hydrocarbyl, silyl,germyl, cyano, halo and combinations thereof, said R³ having up to 20non-hydrogen atoms, or adjacent R³ groups together form a divalentderivative (that is, a hydrocarbadiyl, siladiyl or germadiyl group)thereby forming a fused ring system, and

X″ independently at each occurrence is an anionic ligand group of up to40 non-hydrogen atoms, or two X″ groups together form a divalent anionicligand group of up to 40 non-hydrogen atoms or together are a conjugateddiene having from 4 to 30 non-hydrogen atoms bound by means ofdelocalized π-electrons to M, whereupon M is in the +2 formal oxidationstate, and

R′, E and e are as previously defined.

Exemplary bridged ligands containing two i-bonded groups are:dimethylbis(cyclopentadienyl)silane,dimethylbis(tetramethylcyclopentadienyl)silane,dimethylbis(2-ethylcyclopentadien-1-yl)silane,dimethylbis(2-t-butylcyclopentadien-1-yl)silane,2,2-bis(tetramethylcyclopentadienyl)propane,dimethylbis(inden-1-yl)silane, dimethylbis(tetrahydroinden-1-yl)silane,dimethylbis(fluoren-1-yl)silane,dimethylbis(tetrahydrofluoren-1-yl)silane,dimethylbis(2-methyl-4-phenylinden-1-yl)-silane,dimethylbis(2-methylinden-1-yl)silane,dimethyl(cyclopentadienyl)(fluoren-1-yl)silane,dimethyl(cyclopentadienyl)(octahydrofluoren-1-yl)silane,dimethyl(cyclopentadienyl)(tetrahydrofluoren-1-yl)silane,(1,1,2,2-tetramethy)-1,2-bis(cyclopentadienyl)disilane,(1,2-bis(cyclopentadienyl)ethane, anddimethyl(cyclopentadienyl)-1-(fluoren-1-yl)methane.

Suitable X″ groups are selected from hydride, hydrocarbyl, silyl,germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl andaminohydrocarbyl groups, or two X″ groups together form a divalentderivative of a conjugated diene or else together they form a neutral,π-bonded, conjugated diene. Exemplary X″ groups are C1-20 hydrocarbylgroups.

Examples of metal complexes of the foregoing formula suitable for use inthe present disclosure include:

bis(cyclopentadienyl)zirconiumdimethyl,

bis(cyclopentadienyl)zirconium dibenzyl,

bis(cyclopentadienyl)zirconium methyl benzyl,

bis(cyclopentadienyl)zirconium methyl phenyl,

bis(cyclopentadienyl)zirconiumdiphenyl,

bis(cyclopentadienyl)titanium-allyl,

bis(cyclopentadienyl)zirconiummethylmethoxide,

bis(cyclopentadienyl)zirconiummethylchloride,

bis(pentamethylcyclopentadienyl)zirconiumdimethyl,

bis(pentamethylcyclopentadienyl)titaniumdimethyl,

bis(indenyl)zirconiumdimethyl,

indenylfluorenylzirconiumdimethyl,

bis(indenyl)zirconiummethyl(2-(dimethylamino)benzyl),

bis(indenyl)zirconiummethyltrimethylsilyl,

bis(tetrahydroindenyl)zirconiummethyltrimethylsilyl,

bis(pentamethylcyclopentadienyl)zirconiummethylbenzyl,

bis(pentamethylcyclopentadienyl)zirconiumdibenzyl,

bis(pentamethylcyclopentadienyl)zirconiummethylmethoxide,

bis(pentamethylcyclopentadienyl)zirconiummethylchloride,

bis(methylethylcyclopentadienyl)zirconiumdimethyl,

bis(butylcyclopentadienyl)zirconiumdibenzyl,

bis(t-butylcyclopentadienyl)zirconiumdimethyl,

bis(ethyltetramethylcyclopentadienyl)zirconiumdimethyl,

bis(methylpropylcyclopentadienyl)zirconiumdibenzyl,

bis(trimethylsilylcyclopentadienyl)zirconiumdibenzyl,

dimethylsilylbis(cyclopentadienyl)zirconiumdichloride,

dimethylsilylbis(cyclopentadienyl)zirconiumdimethyl,

dimethylsilylbis(tetramethylcyclopentadienyl)titanium (III) allyl

dimethylsilylbis(t-butylcyclopentadienyl)zirconiumdichloride,

dimethylsilylbis(n-butylcyclopentadienyl)zirconiumdichloride,

(dimethylsilylbis(tetramethylcyclopentadienyl)titanium(III)2-(dimethylamino)benzyl,

(dimethylsilylbis(n-butylcyclopentadienyl)titanium(III)2-(dimethylamino)benzyl,

dimethylsilylbis(indenyl)zirconiumdichloride,

dimethylsilylbis(indenyl)zirconiumdimethyl,

dimethylsilylbis(2-methylindenyl)zirconiumdimethyl,

dimethylsilylbis(2-methyl-4-phenylindenyl)zirconiumdimethyl,

dimethylsilylbis(2-methylindenyl)zirconium-1,4-diphenyl-1,3-butadiene,

dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

dimethylsilylbis(4,5,6,7-tetrahydroinden-1-yl)zirconiumdichloride,

dimethylsilylbis(4,5,6,7-tetrahydroinden-1-yl)zirconiumdimethyl,

dimethylsilylbis(tetrahydroindenyl)zirconium(II)1,4-diphenyl-1,3-butadiene,

dimethylsilylbis(tetramethylcyclopentadienyl)zirconium dimethyl,

dimethylsilylbis(fluorenyl)zirconiumdimethyl,

dimethylsilylbis(tetrahydrofluorenyl)zirconium bis(trimethylsilyl),

ethylenebis(indbnyl)zirconiumdichloride,

ethylenebis(indenyl)zirconiumdimethyl,

ethylenebis(4,5,6,7-tetrahydroindenyl)zirconiumdichloride,

ethylenebis(4,5,6,7-tetrahydroindenyl)zirconiumdimethyl,

(isopropylidene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzyl, and

dimethylsilyl(tetramethylcyclopentadienyl)(fluorenyl)zirconium dimethyl.

A further class of metal complexes utilized in the present disclosurecorresponds to the preceding formula: MKZ_(z)X_(x), or a dimer thereof,wherein M, K, X, x and z are as previously defined, and Z is asubstituent of up to 50 non-hydrogen atoms that together with K forms ametallocycle with M.

Suitable Z substituents include groups containing up to 30 non-hydrogenatoms comprising at least one atom that is oxygen, sulfur, boron or amember of Group 14 of the Periodic Table of the Elements directlyattached to K, and a different atom, selected from the group consistingof nitrogen, phosphorus, oxygen or sulfur that is covalently bonded toM.

More specifically this class of Group 4 metal complexes used accordingto the present invention includes “constrained geometry catalysts”corresponding to the formula:

wherein: M is titanium or zirconium, preferably titanium in the +2, +3,or +4 formal oxidation state;

K¹ is a delocalized, i-bonded ligand group optionally substituted withfrom 1 to 5 R² groups,

R² at each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R² having up to 20 non-hydrogen atoms, oradjacent R² groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system,

each X is a halo, hydrocarbyl, heterohydrocarbyl, hydrocarbyloxy orsilyl group, said group having up to 20 non-hydrogen atoms, or two Xgroups together form a neutral C5-30 conjugated diene or a divalentderivative thereof;

x is 1 or 2;

Y is —O—, —S—, —NR′—, —PR′—;

and X′ is SiR′₂, CR′₂, SiR′₂SiR′₂, CR′₂CR′₂, CR′═CR′, CR′₂SiR′₂, orGeR′₂, wherein

R′ independently at each occurrence is hydrogen or a group selected fromsilyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R′having up to 30 carbon or silicon atoms.

Specific examples of the foregoing constrained geometry metal complexesinclude compounds corresponding to the formula:

wherein,

Ar is an aryl group of from 6 to 30 atoms not counting hydrogen;

R⁴ independently at each occurrence is hydrogen, Ar, or a group otherthan Ar selected from hydrocarbyl, trihydrocarbylsilyl,trihydrocarbylgermyl, halide, hydrocarbyloxy, trihydrocarbylsiloxy,bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino,hydrocarbadiylamino, hydrocarbylimino, di(hydrocarbyl)phosphino,hydrocarbadiylphosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R group having up to 40atoms not counting hydrogen atoms, and optionally two adjacent R⁴ groupsmay be joined together forming a polycyclic fused ring group;

M is titanium;

X′ is SiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶ ₂SiR⁶ ₂,BR⁶, BR⁶L″, or GeR⁶ ₂;

Y is —O—, —S—, —PRS—; —NR⁵ ₂, or —PR⁵ ₂;

R⁵, independently at each occurrence is hydrocarbyl,trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, said R⁵ havingup to 20 atoms other than hydrogen, and optionally two R⁵ groups or R⁵together with Y or Z form a ring system;

R⁶, independently at each occurrence, is hydrogen, or a member selectedfrom hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenatedaryl, —NR⁵ ₂, and combinations thereof, said R⁶ having up to 20non-hydrogen atoms, and optionally, two R⁶ groups or R⁶ together with Zforms a ring system;

Z is a neutral diene or a monodentate or polydentate Lewis baseoptionally bonded to R⁵, R⁶, or X;

X is hydrogen, a monovalent anionic ligand group having up to 60 atomsnot counting hydrogen, or two X groups are joined together therebyforming a divalent ligand group;

x is 1 or 2; and

z is 0, 1 or 2.

Suitable examples of the foregoing metal complexes are substituted atboth the 3- and 4-positions of a cyclopentadienyl or indenyl group withan Ar group. Examples of the foregoing metal complexes include:

(3-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdichloride,

(3-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdimethyl,

(3-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II)1,3-diphenyl-1,3-butadiene;

(3-(pyrrol-1-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdichloride,

(3-(pyrrol-1-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdimethyl,

(3-(pyrrol-1-yl)cyclopentadien-1-yl))dimethyl(t-butylamido)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;

(3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdichloride,

(3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdimethyl,

(3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;

(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdichloride,

(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdimethyl,

(3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II) 1,3-pentadiene;

(3-(3-N,N-dimethylamino)phenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdichloride,

(3-(3-N,N-dimethylamino)phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdimethyl,

(3-(3-N,N-dimethylamino)phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;

(3-(4-methoxyphenyl)-4-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdichloride,

(3-(4-methoxyphenyl)-4-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdimethyl,

(3-4-methoxyphenyl)-4-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;

(3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdichloride,

(3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdimethyl,

(3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;

(3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdichloride,

(3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdimethyl,

(3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;

2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdichloride,

2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdimethyl,

2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;

((2,3-diphenyl)-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium dichloride,

((2,3-diphenyl)-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium dimethyl,

((2,3-diphenyl)-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;

(2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdichloride,

(2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdimethyl,

(2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;

(3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdichloride,

(3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdimethyl,

(3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;

(2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdichloride,

(2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdimethyl,

(2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II) 1,4-diphenyl-1,3-butadiene;

(2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdichloride,

(2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitaniumdimethyl, and(2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium(II) 1,4-diphenyl-1,3-butadiene.

Additional examples of suitable metal complexes herein are polycycliccomplexes corresponding to the formula:

where M is titanium in the +2, +3 or +4 formal oxidation state;

R⁷ independently at each occurrence is hydride, hydrocarbyl, silyl,germyl, halide, hydrocarbyloxy, hydrocarbylsiloxy,hydrocarbylsilylamino, di(hydrocarbyl)amino, hydrocarbyleneamino,di(hydrocarbyl)phosphino, hydrocarbylene-phosphino, hydrocarbylsulfido,halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,silyl-substituted hydrocarbyl, hydrocarbylsiloxy-substitutedhydrocarbyl, hydrocarbylsilylamino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylene-phosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R⁷ group having up to40 atoms not counting hydrogen, and optionally two or more of theforegoing groups may together form a divalent derivative;

R⁸ is a divalent hydrocarbylene- or substituted hydrocarbylene groupforming a fused system with the remainder of the metal complex, said R⁸containing from 1 to 30 atoms not counting hydrogen;

X^(a) is a divalent moiety, or a moiety comprising one σ-bond and aneutral two electron pair able to form a coordinate-covalent bond to M,said X^(a) comprising boron, or a member of Group 14 of the PeriodicTable of the Elements, and also comprising nitrogen, phosphorus, sulfuror oxygen;

X is a monovalent anionic ligand group having up to 60 atoms exclusiveof the class of ligands that are cyclic, delocalized, π-bound ligandgroups and optionally two X groups together form a divalent ligandgroup;

Z independently at each occurrence is a neutral ligating compound havingup to 20 atoms;

x is 0, 1 or 2; and

z is zero or 1.

Suitable examples of such complexes are 3-phenyl-substituted s-indecenylcomplexes corresponding to the formula:

2,3-dimethyl-substituted s-indecenyl complexes corresponding to theformulas:

or 2-methyl-substituted s-indecenyl complexes corresponding to theformula:

Additional examples of metal complexes that are usefully employed ascatalysts according to the present invention include those of theformula:

Specific metal complexes include:

(8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,4-diphenyl-1,3-butadiene,

(8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,3-pentadiene,

(8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (III) 2-(N,N-dimethylamino)benzyl,

(8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (IV) dichloride,

(8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (IV) dimethyl,

(8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (IV) dibenzyl,

(8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,4-diphenyl-1,3-butadiene,

(8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,3-pentadiene,

(8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (III) 2-(N,N-dimethylamino)benzyl,

(8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (IV) dichloride,

(8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (IV) dimethyl,

(8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (IV) dibenzyl,

(8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,4-diphenyl-1,3-butadiene,

(8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,3-pentadiene,

(8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (III) 2-(N,N-dimethylamino)benzyl,

(8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (IV) dichloride,

(8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (IV) dimethyl,

(8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (IV) dibenzyl,

(8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (II) 1,4-diphenyl-1,3-butadiene,

(8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyedimethylsilanamidetitanium (II) 1,3-pentadiene,

(8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (III) 2-(N,N-dimethylamino)benzyl,

(8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (IV) dichloride,

(8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (IV) dimethyl,

(8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamidetitanium (IV) dibenzyl, and mixtures thereof, especially mixtures ofpositional isomers.

Further illustrative examples of metal complexes for use according tothe present invention correspond to the formula:

where M is titanium in the +2, +3 or +4 formal oxidation state;

T is —NR⁹— or —O—;

R⁹ is hydrocarbyl, silyl, germyl, dihydrocarbylboryl, or halohydrocarbylor up to 10 atoms not counting hydrogen;

R¹⁰ independently at each occurrence is hydrogen, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, germyl, halide,hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino,di(hydrocarbyl)amino, hydrocarbyleneamino, di(hydrocarbyl)phosphino,hydrocarbylene-phosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl-substitutedhydrocarbyl, hydrocarbylsiloxy-substituted hydrocarbyl,hydrocarbylsilylamino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R¹⁰ group having up to40 atoms not counting hydrogen atoms, and optionally two or more of theforegoing adjacent R¹⁰ groups may together form a divalent derivativethereby forming a saturated or unsaturated fused ring;

X^(a) is a divalent moiety lacking in delocalized π-electrons, or such amoiety comprising one σ-bond and a neutral two electron pair able toform a coordinate-covalent bond to M, said X^(a) comprising boron, or amember of Group 14 of the Periodic Table of the Elements, and alsocomprising nitrogen, phosphorus, sulfur or oxygen;

X is a monovalent anionic ligand group having up to 60 atoms exclusiveof the class of ligands that are cyclic ligand groups bound to M throughdelocalized π-electrons or two X groups together are a divalent anionicligand group;

Z independently at each occurrence is a neutral ligating compound havingup to 20 atoms;

x is 0, 1, 2, or 3;

and z is 0 or 1.

Illustratively, T is ═N(CH₃), X is halo or hydrocarbyl, x is 2, X^(a) isdimethylsilane, z is 0, and R¹⁰ at each occurrence is hydrogen, ahydrocarbyl, hydrocarbyloxy, dihydrocarbylamino, hydrocarbyleneamino,dihydrocarbylamino-substituted hydrocarbyl group, orhydrocarbyleneamino-substituted hydrocarbyl group of up to 20 atoms notcounting hydrogen, and optionally two R¹⁰ groups may be joined together.

Illustrative metal complexes of the foregoing formula that may beemployed in the practice of the present invention further include thefollowing compounds:

(t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene,

(t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanmm(II) 1,3-pentadiene,

(t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl,

(t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV) dichloride,

(t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV) dimethyl,

(t-butylamido)dimethyl-[6J]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV) dibenzyl,

(t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV) bis(trimethylsilyl),

(cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene,

(cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(II) 1,3-pentadiene,

(cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl,

(cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV) dichloride,

(cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV) dimethyl,

(cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV) dibenzyl,

(cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV) bis(trimethylsilyl),

(t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene,

(t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(II) 1,3-pentadiene,

(t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl,

(t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV) dichloride,

(t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV) dimethyl,

(t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV) dibenzyl,

(t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV) bis(trimethylsilyl),

(cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene,

(cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(II) 1,3-pentadiene,

(cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(III) 2-(N,N-dimethylamino)benzyl,

(cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV) dichloride,

(cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV) dimethyl,

(cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV) dibenzyl; and

(cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium(IV) bis(trimethylsilyl).

Illustrative Group 4 metal complexes that may be employed in thepractice of the present disclosure further include:

(tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl(tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium dibenzyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitaniumdimethyl,

(tert-butylamido)(tetramethyl-η⁵-indenyl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (III) 2-(dimethylamino)benzyl;

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(III) allyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(III) 2,4-dimethylpentadienyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II) 1,3-pentadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)1,4-diphenyl-1,3-butadiene,(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)2,4-hexadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV) 2,3-dimethyl-1,3-butadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) isoprene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) 1,3-butadiene,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)2,3-dimethyl-1,3-butadiene,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)isoprene,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)dimethyl,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)dibenzyl,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)1,3-butadiene,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II)1,3-pentadiene,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II)1,4-diphenyl-1,3-butadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)1,3-pentadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) dimethyl,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) dibenzyl,

(tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II)1,4-diphenyl-1,3 -butadiene,

(tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II)1,3-pentadiene,

(tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II)2,4-hexadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium(IV) 1,3 -butadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(IV) 2,3 -dimethyl-1,3-butadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(IV) isoprene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium(II) 1,4-dibenzyl-1,3-butadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(II) 2,4-hexadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium(II) 3-methyl-1,3-pentadiene,

(tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethylsilanetitaniumdimethyl,(tert-butylamido)(6,6-dimethylcyclohexadienyl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienylmethylphenylsilanetitanium (IV) dimethyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienylmethylphenylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene,

1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyltitanium(IV) dimethyl, and

1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyl-titanium(II) 1,4-diphenyl-1,3-butadiene.

Other delocalized, π-bonded complexes, especially those containing otherGroup 4 metals, will, of course, be apparent to those skilled in theart, and are disclosed among other places in: WO 03/78480, WO 03/78483,WO 02/92610, WO 02/02577, US 2003/0004286 and U.S. Pat. Nos. 6,515,155,6,555,634, 6,150,297, 6,034,022, 6,268,444, 6,015,868, 5,866,704, and5,470,993.

Additional examples of metal complexes that are usefully employed ascatalysts are complexes of polyvalent Lewis bases, such as compoundscorresponding to the formula:

wherein T^(b) is a bridging group, preferably containing 2 or more atomsother than hydrogen,

X^(b) and Y^(b) are each independently selected from the groupconsisting of nitrogen, sulfur, oxygen and phosphorus; more preferablyboth X^(b) and Y^(b) are nitrogen,

R^(b) and R^(b′) independently each occurrence are hydrogen or C₁₋₅₀hydrocarbyl groups optionally containing one or more heteroatoms orinertly substituted derivative thereof. Non-limiting examples ofsuitable R^(b) and R^(b′) groups include alkyl, alkenyl, aryl, aralkyl,(poly)alkylaryl and cycloalkyl groups, as well as nitrogen, phosphorus,oxygen and halogen substituted derivatives thereof. Specific examples ofsuitable Rb and Rb′ groups include methyl, ethyl, isopropyl, octyl,phenyl, 2,6-dimethylphenyl, 2,6-di(isopropyl)phenyl,2,4,6-trimethylphenyl, pentafluorophenyl, 3,5-trifluoromethylphenyl, andbenzyl;

g and g′ are each independently 0 or 1;

M^(b) is a metallic element selected from Groups 3 to 15, or theLanthanide series of the Periodic Table of the Elements. Preferably,M^(b) is a Group 3-13 metal, more preferably M^(b) is a Group 4-10metal;

L^(b) is a monovalent, divalent, or trivalent anionic ligand containingfrom 1 to 50 atoms, not counting hydrogen. Examples of suitable L^(b)groups include halide; hydride; hydrocarbyl, hydrocarbyloxy;di(hydrocarbyl)amido, hydrocarbyleneamido, di(hydrocarbyl)phosphido;hydrocarbylsulfido; hydrocarbyloxy, tri(hydrocarbylsilyl)alkyl; andcarboxylates. More preferred L^(b) groups are C1-20 alkyl, C₇₋₂₀aralkyl, and chloride;

h and h′ are each independently an integer from 1 to 6, preferably from1 to 4, more preferably from 1 to 3, and j is 1 or 2, with the value h×jselected to provide charge balance;

Z^(b) is a neutral ligand group coordinated to M^(b), and containing upto 50 atoms not counting hydrogen. Preferred Z^(b) groups includealiphatic and aromatic amines, phosphines, and ethers, alkenes,alkadienes, and inertly substituted derivatives thereof. Suitable inertsubstituents include halogen, alkoxy, aryloxy, alkoxycarbonyl,aryloxycarbonyl, di(hydrocarbyl)amine, tri(hydrocarbyl)silyl, andnitrile groups. Preferred Z^(b) groups include triphenylphosphine,tetrahydrofuran, pyridine, and 1,4-diphenylbutadiene;

f is an integer from 1 to 3;

two or three of T^(b), R^(b) and R^(b′) may be joined together to form asingle or multiple ring structure;

h is an integer from 1 to 6, preferably from 1 to 4, more preferablyfrom 1 to 3;

indicates any form of electronic interaction, especially coordinate orcovalent bonds, including multiple bonds, arrows signify coordinatebonds, and dotted lines indicate optional double bonds.

In one embodiment, it is preferred that R^(b) have relatively low sterichindrance with respect to X^(b). In this embodiment, most preferredR^(b) groups are straight chain alkyl groups, straight chain alkenylgroups, branched chain alkyl groups wherein the closest branching pointis at least 3 atoms removed from X^(b), and halo, dihydrocarbylamino,alkoxy or trihydrocarbylsilyl substituted derivatives thereof. Highlypreferred R^(b) groups in this embodiment are C1-8 straight chain alkylgroups.

At the same time, in this embodiment R^(b)′ preferably has relativelyhigh steric hindrance with respect to Y^(b). Non-limiting examples ofsuitable R^(b)′ groups for this embodiment include alkyl or alkenylgroups containing one or more secondary or tertiary carbon centers,cycloalkyl, aryl, alkaryl, aliphatic or aromatic heterocyclic groups,organic or inorganic oligomeric, polymeric or cyclic groups, and halo,dihydrocarbylamino, alkoxy or trihydrocarbylsilyl substitutedderivatives thereof. Preferred R^(b)′ groups in this embodiment containfrom 3 to 40, more preferably from 3 to 30, and most preferably from 4to 20 atoms not counting hydrogen and are branched or cyclic. Examplesof preferred T^(b) groups are structures corresponding to the followingformulas:

wherein

Each R^(d) is C1-10 hydrocarbyl group, preferably methyl, ethyl,n-propyl, propyl, t-butyl, phenyl, 2,6-dimethylphenyl, benzyl, or tolyl.Each R^(e) is C1-10 hydrocarbyl, preferably methyl, ethyl, n-propyl,i-propyl, t-butyl, phenyl, 2,6-dimethylphenyl, benzyl, or tolyl. Inaddition, two or more R^(d) or R^(e) groups, or mixtures of R^(d) andR^(e) groups may together form a polyvalent derivative of a hydrocarbylgroup, such as, 1,4-butylene, 1,5-pentylene, or a multicyclic, fusedring, polyvalent hydrocarbyl- or heterohydrocarbyl-group, such asnaphthalene-1,8-diyl.

Suitable examples of the foregoing polyvalent Lewis base complexesinclude:

wherein R^(d′) at each occurrence is independently selected from thegroup consisting of hydrogen and C1-50 hydrocarbyl groups optionallycontaining one or more heteroatoms, or inertly substituted derivativethereof, or further optionally, two adjacent R^(d′) groups may togetherform a divalent bridging group;

d′ is 4;

M^(b′) is a Group 4 metal, preferably titanium or hafnium, or a Group 10metal, preferably Ni or Pd;

L^(b′) is a monovalent ligand of up to 50 atoms not counting hydrogen,preferably halide or hydrocarbyl, or two L^(b′) groups together are adivalent or neutral ligand group, preferably a C₂₋₅₀ hydrocarbylene,hydrocarbadiyl or diene group.

The polyvalent Lewis base complexes for use in the present inventionespecially include Group 4 metal derivatives, especially hafniumderivatives of hydrocarbylamine substituted heteroaryl compoundscorresponding to the formula:

wherein:

R¹¹ is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl,aryl, and inertly substituted derivatives thereof containing from 1 to30 atoms not counting hydrogen or a divalent derivative thereof;

T¹ is a divalent bridging group of from 1 to 41 atoms other thanhydrogen, preferably 1 to 20 atoms other than hydrogen, and mostpreferably a mono- or di-C1-20 hydrocarbyl substituted methylene orsilane group; and

R¹² is a C₅₋₂₀ heteroaryl group containing Lewis base functionality,especially a pyridin-2-yl- or substituted pyridin-2-yl group or adivalent derivative thereof;

M¹ is a Group 4 metal, preferably hafnium;

X¹ is an anionic, neutral or dianionic ligand group;

x′ is a number from 0 to 5 indicating the number of such X¹ groups; andbonds, optional bonds and electron donative interactions are representedby lines, dotted lines and arrows respectively.

Suitable complexes are those wherein ligand formation results fromhydrogen elimination from the amine group and optionally from the lossof one or more additional groups, especially from R¹². In addition,electron donation from the Lewis base functionality, preferably anelectron pair, provides additional stability to the metal center.Suitable metal complexes correspond to the formula:

wherein M¹, X¹, x′, R¹¹ and T¹ are as previously defined,

R¹³, R¹⁴, R¹⁵ and R¹⁶ are hydrogen, halo, or an alkyl, cycloalkyl,heteroalkyl, heterocycloalkyl, aryl, or silyl group of up to 20 atomsnot counting hydrogen, or adjacent R¹³, R¹⁴, R¹⁵ or R¹⁶ groups may bejoined together thereby forming fused ring derivatives, and bonds,optional bonds and electron pair donative interactions are representedby lines, dotted lines and arrows respectively. Suitable examples of theforegoing metal complexes correspond to the formula:

wherein

M¹, X¹, and x′ are as previously defined,

R¹³, R¹⁴, R¹⁵ and R¹⁶ are as previously defined, preferably R¹³, R¹⁴,and R¹⁵ are hydrogen, or C1-4 alkyl, and R¹⁶ is C₆₋₂₀ aryl, mostpreferably naphthalenyl;

R^(a) independently at each occurrence is C₁₋₄ alkyl, and a is 1-5, mostpreferably R^(a) in two ortho-positions to the nitrogen is isopropyl ort-butyl;

R¹⁷ and R¹⁸ independently at each occurrence are hydrogen, halogen, or aC₁₋₂₀ alkyl or aryl group, most preferably one of R¹⁷ and R¹⁸ ishydrogen and the other is a C6-20 aryl group, especially 2-isopropyl,phenyl or a fused polycyclic aryl group, most preferably an anthracenylgroup, and bonds, optional bonds and electron pair donative interactionsare represented by lines, dotted lines and arrows respectively.

Exemplary metal complexes for use herein as catalysts correspond to theformula:

wherein X¹ at each occurrence is halide, N,N-dimethylamido, or C₁₋₄alkyl, and preferably at each occurrence X¹ is methyl;

R^(f) independently at each occurrence is hydrogen, halogen, C1-20alkyl, or C6-20 aryl, or two adjacent R^(f) groups are joined togetherthereby forming a ring, and f is 1-5; and

R^(e) independently at each occurrence is hydrogen, halogen, C₁₋₂₀alkyl, or C₆₋₂₀ aryl, or two adjacent R^(c) groups are joined togetherthereby forming a ring, and c is 1-5.

Suitable examples of metal complexes for use as catalysts according tothe present invention are complexes of the following formulas:

wherein R^(x) is C1-4 alkyl or cycloalkyl, preferably methyl, isopropyl,t-butyl or cyclohexyl; and

X¹ at each occurrence is halide, N,N-dimethylamido, or C1-4 alkyl,preferably methyl.

Examples of metal complexes usefully employed as catalysts according tothe present invention include:

[N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalen-2-diyl(6-pyridin-2-diyemethane)]hafniumdimethyl;

[N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalen-2-diyl(6-pyridin-2-diyemethane)]hafhiumdi(N,N-dimethylamido);

[N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalen-2-diyl(6-pyridin-2-diyemethane)]hafniumdichloride;

[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyemethane)]hafniumdimethyl;

[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyemethane)]hafniumdi(N,N-dimethylamido);

[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyemethane)]hafniumdichloride;

[N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalen-2-diyl(6-pyridin-2-diyemethane)]hafhiumdimethyl;

[N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalen-2-diyl(6-pyridin-2-diyemethane)]hafhiumdi(N,N-dimethylamido); and

[N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalen-2-diyl(6-pyridin-2-diyemethane)]hafniumdichloride.

Under the reaction conditions used to prepare the metal complexes usedin the present disclosure, the hydrogen of the 2-position of thea-naphthalene group substituted at the 6-position of the pyridin-2-ylgroup is subject to elimination, thereby uniquely forming metalcomplexes wherein the metal is covalently bonded to both the resultingamide group and to the 2-position of the α-naphthalenyl group, as wellas stabilized by coordination to the pyridinyl nitrogen atom through theelectron pair of the nitrogen atom.

Additional suitable metal complexes of polyvalent Lewis bases for useherein include compounds corresponding to the formula:

wherein:

R²⁰ is an aromatic or inertly substituted aromatic group containing from5 to 20 atoms not counting hydrogen, or a polyvalent derivative thereof;

T³ is a hydrocarbylene or hydrocarbyl silane group having from 1 to 20atoms not counting hydrogen, or an inertly substituted derivativethereof;

M³ is a Group 4 metal, preferably zirconium or hafnium;

G is an anionic, neutral or dianionic ligand group; preferably a halide,hydrocarbyl, silane, trihydrocarbylsilylhydrocarbyl,trihydrocarbylsilyl, or dihydrocarbylamide group having up to 20 atomsnot counting hydrogen;

g is a number from 1 to 5 indicating the number of such G groups; andbonds and electron donative interactions are represented by lines andarrows respectively.

Illustratively, such complexes correspond to the formula:

wherein:

T³ is a divalent bridging group of from 2 to 20 atoms not countinghydrogen, preferably a substituted or unsubstituted, C3-6 alkylenegroup;

and Ar² independently at each occurrence is an arylene or an alkyl- oraryl-substituted arylene group of from 6 to 20 atoms not countinghydrogen;

M³ is a Group 4 metal, preferably hafnium or zirconium;

G independently at each occurrence is an anionic, neutral or dianionicligand group;

g is a number from 1 to 5 indicating the number of such X groups; andelectron donative interactions are represented by arrows.

Suitable examples of metal complexes of foregoing formula include thefollowing compounds

where M³ is Hf or Zr;

Ar⁴ is C₆₋₂₀ aryl or inertly substituted derivatives thereof, especially3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl,dibenzo-1H-pyrrole-1-yl, or anthracen-5-yl, and

T⁴ independently at each occurrence comprises a C₃₋₆ alkylene group, aC₃₋₆ cycloalkylene group, or an inertly substituted derivative thereof;

R²¹ independently at each occurrence is hydrogen, halo, hydrocarbyl,trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl of up to 50 atomsnot counting hydrogen; and

G, independently at each occurrence is halo or a hydrocarbyl ortrihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2G groups together are a divalent derivative of the foregoing hydrocarbylor trihydrocarbylsilyl groups.

Suitable compounds are compounds of the formulas:

wherein Ar⁴ is 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl,dibenzo-1H-pyrrole-1-yl, or anthracen-5-yl,

R²¹ is hydrogen, halo, or C1-4 alkyl, especially methyl

T⁴ is propan-1,3-diyl or butan-1,4-diyl, and

G is chloro, methyl or benzyl.

An exemplary metal complex of the foregoing formula is:

Suitable metal complexes for use according to the present disclosurefurther include compounds corresponding to the formula:

where:

M is zirconium or hafnium;

R²⁰ independently at each occurrence is a divalent aromatic or inertlysubstituted aromatic group containing from 5 to 20 atoms not countinghydrogen;

T³ is a divalent hydrocarbon or silane group having from 3 to 20 atomsnot counting hydrogen, or an inertly substituted derivative thereof; and

R^(D) independently at each occurrence is a monovalent ligand group offrom 1 to 20 atoms, not counting hydrogen, or two R^(D) groups togetherare a divalent ligand group of from 1 to 20 atoms, not countinghydrogen.

Such complexes may correspond to the formula:

wherein:

Ar² independently at each occurrence is an arylene or an alkyl-, aryl-,alkoxy- or amino-substituted arylene group of from 6 to 20 atoms notcounting hydrogen or any atoms of any substituent;

T³ is a divalent hydrocarbon bridging group of from 3 to 20 atoms notcounting hydrogen, preferably a divalent substituted or unsubstitutedC₃₋₆ aliphatic, cycloaliphatic, or bis(alkylene)-substitutedcycloaliphatic group having at least 3 carbon atoms separating oxygenatoms; and

R^(D) independently at each occurrence is a monovalent ligand group offrom 1 to 20 atoms, not counting hydrogen, or two R^(D) groups togetherare a divalent ligand group of from 1 to 40 atoms, not countinghydrogen.

Further examples of metal complexes suitable for use herein includecompounds of the formula:

where

Ar⁴ independently at each occurrence is C₆₋₂₀ aryl or inertlysubstituted derivatives thereof, especially 3,5-di(isopropyl)phenyl,3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrole-1-yl, naphthyl,anthracen-5-yl, 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl;

T⁴ independently at each occurrence is a propylene-1,3-diyl group, abis(alkylene)cyclohexan-1,2-diyl group, or an inertly substitutedderivative thereof substituted with from 1 to 5 alkyl, aryl or aralkylsubstituents having up to 20 carbons each;

R²¹ independently at each occurrence is hydrogen, halo, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino ofup to 50 atoms not counting hydrogen; and

R^(D), independently at each occurrence is halo or a hydrocarbyl ortrihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2R^(D) groups together are a divalent hydrocarbylene, hydrocarbadiyl ortrihydrocarbylsilyl group of up to 40 atoms not counting hydrogen.

Exemplary metal complexes are compounds of the formula:

where, Ar⁴, independently at each occurrence, is3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl,dibenzo-1H-pyrrole-1-yl, or anthracen-5-yl,

R²¹ independently at each occurrence is hydrogen, halo, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino ofup to 50 atoms not counting hydrogen;

T⁴ is propan-1,3-diyl or bis(methylene)cyclohexan-1,2-diyl; and

R^(D), independently at each occurrence is halo or a hydrocarbyl ortrihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2R^(D) groups together are a hydrocarbylene, hydrocarbadiyl orhydrocarbylsilanediyl group of up to 40 atoms not counting hydrogen.

Suitable metal complexes according to the present disclosure correspondto the formulas:

wherein, R^(D) independently at each occurrence is chloro, methyl orbenzyl.

Specific examples of suitable metal complexes are the followingcompounds:

-   A) bis((2-oxoyl-3    -(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV)    dibenzyl,-   B)    bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV)    dibenzyl,-   C)    bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV)    dibenzyl,-   D)    bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV)    dichloride, and-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV)    dibenzyl.

The foregoing metal complexes may be conveniently prepared by standardmetallation and ligand exchange procedures involving a source of thetransition metal and a neutral polyfunctional ligand source. Thetechniques employed are the same as or analogous to those disclosed inU.S. Pat. No. 6,827,976 and US2004/0010103, and elsewhere.

The metal complex is activated to form the active catalyst compositionby combination with the cocatalyst. The activation may occur prior toaddition of the catalyst composition to the reactor with or without thepresence of other components of the reaction mixture, or in situ throughseparate addition of the metal complex and activating cocatalyst to thereactor.

The foregoing polyvalent Lewis base complexes are conveniently preparedby standard metallation and ligand exchange procedures involving asource of the Group 4 metal and the neutral polyfunctional ligandsource. In addition, the complexes may also be prepared by means of anamide elimination and hydrocarbylation process starting from thecorresponding Group 4 metal tetraamide and a hydrocarbylating agent,such as trimethylaluminum. Other techniques may be used as well. Thesecomplexes are known from the disclosures of, among others, U.S. Pat.Nos. 6,320,005, 6,103,657, WO 02/38628, WO 03/40195, and US 04/0220050.

Catalysts having high comonomer incorporation properties are also knownto reincorporate in situ prepared long chain olefins resultingincidentally during the polymerization through β-hydride elimination andchain termination of growing polymer, or other process. Theconcentration of such long chain olefins is particularly enhanced by useof continuous solution polymerization conditions at high conversions,especially ethylene conversions of 95 percent or greater, morepreferably at ethylene conversions of 97 percent or greater. Under suchconditions a small but detectable quantity of olefin terminated polymermay be reincorporated into a growing polymer chain, resulting in theformation of long chain branches, that is, branches of a carbon lengthgreater than would result from other deliberately added comonomer.Moreover, such chains reflect the presence of other comonomers presentin the reaction mixture. That is, the chains may include short chain orlong chain branching as well, depending on the comonomer composition ofthe reaction mixture. Long chain branching of olefin polymers is furtherdescribed in U.S. Pat. Nos. 5,272,236, 5,278,272, and 5,665,800.

Alternatively, branching, including hyper-branching, may be induced in aparticular segment of the present multi-block copolymers by the use ofspecific catalysts known to result in “chain-walking” in the resultingpolymer. For example, certain homogeneous bridged bis indenyl- orpartially hydrogenated bis indenyl-zirconium catalysts, disclosed byKaminski, et al., J. Mol. Catal. A: Chemical, 102 (1995) 59-65;Zambelli, et al., Macromolecules, 1988, 21, 617-622; or Dias, et al., J.Mol. Catal. A: Chemical, 185 (2002) 57-64 may be used to preparebranched copolymers from single monomers, including ethylene. Highertransition metal catalysts, especially nickel and palladium catalystsare also known to lead to hyper-branched polymers (the branches of whichare also branched) as disclosed in Brookhart, et al., J. Am. Chem. Soc.,1995, 117, 64145-6415.

Additional complexes suitable for use include Group 4-10 derivativescorresponding to the formula:

wherein

M² is a metal of Groups 4-10 of the Periodic Table of the elements,preferably Group 4 metals, Ni(II) or Pd(II), most preferably zirconium;

T² is a nitrogen, oxygen or phosphorus containing group;

X² is halo, hydrocarbyl, or hydrocarbyloxy;

t is one or two;

x″ is a number selected to provide charge balance;

and T² and N are linked by a bridging ligand.

Such catalysts have been previously disclosed in J. Am. Chem. Soc., 118,267-268 (1996), J. Am. Chem. Soc., 117, 6414-6415 (1995), andOrganometallics, 16, 1514-1516, (1997), among other disclosures.

Suitable examples of the foregoing metal complexes for use as catalystsare aromatic diimine or aromatic dioxyimine complexes of Group 4 metals,especially zirconium, corresponding to the formula:

wherein;

M², X² and T² are as previously defined;

R^(d) independently in each occurrence is hydrogen, halogen, or R^(e);and

R^(e) independently in each occurrence is C1-20 hydrocarbyl or aheteroatom-, especially a F, N, S or P-substituted derivative thereof,more preferably C1-20 hydrocarbyl or a F or N substituted derivativethereof, most preferably alkyl, dialkylaminoalkyl, pyrrolyl,piperidenyl, perfluorophenyl, cycloalkyl, (poly)alkylaryl, or aralkyl.

Suitable examples of the foregoing metal complexes for use as catalystsare aromatic dioxyimine complexes of zirconium, corresponding to theformula:

wherein;

X² is as previously defined, preferably C1-10 hydrocarbyl, mostpreferably methyl or benzyl; and

R^(e′) is methyl, isopropyl, t-butyl, cyclopentyl, cyclohexyl,2-metltylcyclohexyl, 2,4-dimethylcyclohexyl, 2-pyrrolyl,N-methyl-2-pyrrolyl, 2-piperidenyl, N-methyl-2-piperidenyl, benzyl,o-tolyl, 2,6-dimethylphenyl, perfluorophenyl, 2,6-di(isopropyl)phenyl,or 2,4,6-trimethylphenyl.

The foregoing complexes for use as also include certain phosphiniminecomplexes are disclosed in EP-A-890581. These complexes correspond tothe formula: └(R^(f))₃—P═N┘_(f)M(K²)(R^(f))_(3-f), wherein: R^(f) is amonovalent ligand or two R^(f) groups together are a divalent ligand,preferably R^(f) is hydrogen or C1-4 alkyl;

M is a Group 4 metal,

K² is a group containing delocalized π-electrons through which K² isbound to

M, said K² group containing up to 50 atoms not counting hydrogen atoms,and f is 1 or 2.

With reference to the above discussion of the process for preparing thecomposition having the formula (I), the catalyst precursor (incombination with the co-catalyst) may remain active in the finalsolution and can further function as an active catalyst in subsequentpolymerization. Accordingly, the final solution of the process of thepresent disclosure (the final solution comprising the catalyst and thecomposition having the formula (I)) can be directly used for olefinpolymerization without any isolation, purification, or separationrequirements and without the requirement of having a removable supportedcatalyst.

Exemplary, non-limiting catalyst precursors for the present disclosureinclude any catalyst having good chain transfer ability withorganometallic compounds. Exemplary, non-limiting catalyst precursorsshould have no detrimental effect on subsequent polymerization and,therefore, need not be removed from the final solution prior to olefinpolymerization. Exemplary, non-limiting catalyst precursors may be goodcomonomer incorporating catalysts, can be used to make the compositionshaving the formula (I), and can also continue to remain active (incombination with co-catalyst) as active catalysts to make desiredpolymers in polymerization reactors, as discussed below.

Exemplary catalyst precursors that can be used in accordance with thepresent disclosure include but are not limited to Catalysts (A1)-(A7),as listed below.

Catalyst (A1):[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl] prepared according to the teachings of WO 03/40195 and WO04/24740 as well as methods known in the art.

Catalyst (A2):(E)-((2,6-diisopropylphenyl)(2-methyl-3-(octylimino)butan-2-yl)amino)trimethylhafnium prepared according to methods known in the art.

Catalyst (A3):[[2′,2′″-[1,2-cyclohexanediylbis(methyleneoxy-κO)]bis[3-(9H-carbazol-9-yl)-5-methyl[1,1′-biphenyl]-2-olato-κO]](2-)]dimethylhafnium prepared according to methods known in the art.

Catalyst (A4):[[2′,2′″-[1,4-butanediylbis(oxy-κO)]bis[3-(9H-carbazol-9-yl)-3′-fluoro-5-methyl[1,1′-biphenyl]-2-olato-κO]](2-)]-dimethylhafnium prepared according to methods known in the art.

Catalyst (A5): Cyclopentadienylbis((trimethylsilyl)methyl)scandiumtetrahydrofuran complex prepared according to methods known in the art.

Catalyst (A6): (Mesityl(pyridin-2-ylmethyl)amino)tribenzyl hafniumprepared according to methods known in the art.

Catalyst (A7):(N-((6E)-6-(Butylimino-κN)-1-cyclohexen-1-yl)-2,6-bis(1-methylethyl)benzenaminato-κN)trimethyl-hafniumprepared according to the disclosures of WO2010/022228 as well asmethods known in the art.

Co-Catalyst

Each of the catalyst precursors of the present disclosure may beactivated to form an active catalyst composition by combination with aco-catalyst, preferably a cation forming co-catalyst, a strong Lewisacid, or a combination thereof. Thus, this disclosure also provides forthe use of at least one co-catalyst in a catalyst composition andvarious methods, along with at least one catalyst precursor, and thecomposition having the formula (I) as disclosed herein.

The catalyst precursors desirably are rendered catalytically active bycombination with a cation forming cocatalyst. Suitable cation formingco-catalysts include those previously known in the art for metal olefinpolymerization complexes. Examples include neutral Lewis acids, such asC₁₋₃₀ hydrocarbyl substituted Group 13 compounds, especiallytri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds andhalogenated (including perhalogenated) derivatives thereof, having from1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group,more especially perfluorinated tri(aryl)boron compounds, and mostespecially tris(pentafluoro-phenyl)borane; nonpolymeric, compatible,noncoordinating, ion forming compounds (including the use of suchcompounds under oxidizing conditions), especially the use of ammonium-,phosphonium-, oxonium-, carbonium-, silylium- or sulfonium-salts ofcompatible, noncoordinating anions, or ferrocenium-, lead- or silversalts of compatible, noncoordinating anions; and combinations of theforegoing cation forming cocatalysts and techniques. The foregoingactivating co-catalysts and activating techniques have been previouslytaught with respect to different metal complexes for olefinpolymerizations in the following references: EP-A-277,003; U.S. Pat.Nos. 5,153,157; 5,064,802; 5,321,106; 5,721,185; 5,350,723; 5,425,872;5,625,087; 5,883,204; 5,919,983; 5,783,512; WO 99/15534, and WO99/42467.

Combinations of neutral Lewis acids, especially the combination of atrialkyl aluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to20 carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, further combinations of such neutralLewis acid mixtures with a polymeric or oligomeric alumoxane, andcombinations of a single neutral Lewis acid, especiallytris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxanemay be used as activating cocatalysts. Exemplary molar ratios of metalcomplex:tris(pentafluorophenyl-borane:alumoxane are from 1:1:1 to1:5:20, such as from 1:1:1.5 to 1:5:10.

Suitable ion forming compounds useful as co-catalysts in one embodimentof the present disclosure comprise a cation which is a Brønsted acidcapable of donating a proton, and a compatible, noncoordinating anion,A⁻. As used herein, the term “noncoordinating” refers to an anion orsubstance which either does not coordinate to the Group 4 metalcontaining precursor complex and the catalytic derivative derived therefrom, or which is only weakly coordinated to such complexes therebyremaining sufficiently labile to be displaced by a neutral Lewis base. Anoncoordinating anion specifically refers to an anion which whenfunctioning as a charge balancing anion in a cationic metal complex doesnot transfer an anionic substituent or fragment thereof to said cationthereby forming neutral complexes. “Compatible anions” are anions whichare not degraded to neutrality when the initially formed complexdecomposes and are noninterfering with desired subsequent polymerizationor other uses of the complex.

Suitable anions are those containing a single coordination complexcomprising a charge-bearing metal or metalloid core which anion iscapable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitriles. Suitable metals include,but are not limited to, aluminum, gold and platinum. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, and silicon.Compounds containing anions which comprise coordination complexescontaining a single metal or metalloid atom are, of course, well knownand many, particularly such compounds containing a single boron atom inthe anion portion, are available commercially.

In one aspect, suitable cocatalysts may be represented by the followinggeneral formula:

(L*-H)_(g) ⁺(A)^(g−), wherein:

L* is a neutral Lewis base;

(L*-H)⁺ is a conjugate Brønsted acid of L*;

A^(g−) is a noncoordinating, compatible anion having a charge of g−, andg is an integer from 1 to 3.

More particularly, A^(g−) corresponds to the formula: [M′Q₄]⁻; wherein:

M′ is boron or aluminum in the +3 formal oxidation state; and

Q independently in each occurrence is selected from hydride,dialkyl-amido, halide, hydrocarbyl, hydrocarbyloxide,halosubstituted-hydrocarbyl, halosubstituted hydrocarbyloxy, andhalo-substituted silylhydrocarbyl radicals (including perhalogenatedhydrocarbyl-perhalogenated hydrocarbyloxy- and perhalogenatedsilylhydrocarbyl radicals), each Q having up to 20 carbons with theproviso that in not more than one occurrence is Q halide. Examples ofsuitable hydrocarbyloxide Q groups are disclosed in U.S. Pat. No.5,296,433.

In an exemplary embodiment, d is one, that is, the counter ion has asingle negative charge and is A⁻. Activating cocatalysts comprisingboron which are particularly useful in the preparation of catalysts ofthis disclosure may be represented by the following general formula:

-   (L*-H)⁺(BQ₄)⁻; wherein:

L* is as previously defined;

B is boron in a formal oxidation state of 3; and

Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-,fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl-group of upto 20 nonhydrogen atoms, with the proviso that in not more than oneoccasion is Q hydrocarbyl.

Especially useful Lewis base salts are ammonium salts, more preferablytrialkyl-ammonium salts containing one or more C₁₂₋₄₀ alkyl groups. Inthis aspect, for example, Q in each occurrence can be a fluorinated arylgroup, especially, a pentafluorophenyl group.

Illustrative, but not limiting, examples of boron compounds which may beused as an activating cocatalyst in the preparation of the improvedcatalysts of this disclosure include the tri-substituted ammonium saltssuch as:

trimethylammonium tetrakis(pentafluorophenyl)borate,

triethylammonium tetrakis(pentafluorophenyl)borate,

tripropylammonium tetrakis(pentafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,

tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,

N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate,

N,N-dimethylanilinium benzyltris(pentafluorophenyl)borate,

N,N-dimethylanilinium tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6tetrafluorophenyl)borate,

N,N-dimethylaniliniumtetrakis(4-(triisopropylsilyl)-2,3,5,6-tetrafluorophenyl)borate,

N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl)borate,

N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate,

dimethyloctadecylammonium tetrakis(pentafluorophenyl)borate,

methyldioctadecylammonium tetrakis(pentafluorophenyl)borate;

a number of dialkyl ammonium salts such as:

di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,

methyloctadecylammonium tetrakis(pentafluorophenyl)borate,

methyloctadodecylammonium tetrakis(pentafluorophenyl)borate, and

dioctadecylammonium tetrakis(pentafluorophenyl)borate;

various tri-substituted phosphonium salts such as:

triphenylphosphonium tetrakis(pentafluorophenyl)borate,

methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate, and

tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate;

di-substituted oxonium salts such as:

diphenyloxonium tetrakis(pentafluorophenyl)borate,

di(o-tolyl)oxonium tetrakis(pentafluorophenyl)borate, and

di(octadecyl)oxonium tetrakis(pentafluorophenyl)borate; and

di-substituted sulfonium salts such as:

di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate, and

methylcotadecylsulfonium tetrakis(pentafluorophenyl)borate.

Further to this aspect of the disclosure, examples of useful (L*-H)⁺cations include, but are not limited to, methyldioctadecylammoniumcations, dimethyloctadecylammonium cations, and ammonium cations derivedfrom mixtures of trialkyl amines containing one or two C₁₄₋₁₈ alkylgroups.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:

(Ox^(h+))_(g)(A^(g−))_(h), wherein:

Ox^(h+) is a cationic oxidizing agent having a charge of h+;

h is an integer from 1 to 3; and

A^(g−) and g are as previously defined.

Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Particularly usefulexamples of A^(g−) are those anions previously defined with respect tothe Bronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst can be a compoundwhich is a salt of a carbenium ion and a noncoordinating, compatibleanion represented by the following formula:

[C]⁺A⁻

wherein:

[C]⁺ is a C₁₋₂₀ carbenium ion; and

is a noncoordinating, compatible anion having a charge of −1. Forexample, one carbenium ion that works well is the trityl cation, that istriphenylmethylium.

A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:

(Q¹ ₃Si)⁺A⁻

wherein:

Q¹ is C₁₋₁₀ hydrocarbyl, and A⁻ is as previously defined.

Suitable silylium salt activating cocatalysts include trimethylsilyliumtetrakispentafluorophenylborate, triethylsilyliumtetrakispentafluorophenylborate, and ether substituted adducts thereof.Silylium salts have been previously generically disclosed in J. Chem.Soc. Chem. Comm. 1993, 383-384, as well as in Lambert, J. B., et al.,Organometallics 1994, 13, 2430-2443. The use of the above silylium saltsas activating cocatalysts for addition polymerization catalysts is alsodescribed in U.S. Pat. No. 5,625,087.

Certain complexes of alcohols, mercaptans, silanols, and oximes withtris(pentafluorophenyl)borane are also effective catalyst activators andmay be used according to the present disclosure. Such cocatalysts aredisclosed in U.S. Pat. No. 5,296,433.

Suitable activating cocatalysts for use herein also include polymeric oroligomeric alumoxanes (also called aluminoxanes), especiallymethylalumoxane (MAO), triisobutyl aluminum modified methylalumoxane(MMAO), or isobutylalumoxane; Lewis acid modified alumoxanes, especiallyperhalogenated tri(hydrocarbyl)aluminum- or perhalogenatedtri(hydrocarbyl)boron modified alumoxanes, having from 1 to 10 carbonsin each hydrocarbyl or halogenated hydrocarbyl group, and mostespecially tris(pentafluorophenyl)borane modified alumoxanes. Suchco-catalysts are previously disclosed in U.S. Pat. Nos. 6,214,760,6,160,146, 6,140,521, and 6,696,379.

A class of co-catalysts comprising non-coordinating anions genericallyreferred to as expanded anions, further disclosed in U.S. Pat. No.6,395,671, may be suitably employed to activate the metal complexes ofthe present disclosure for olefin polymerization. Generally, theseco-catalysts (illustrated by those having imidazolide, substitutedimidazolide, imidazolinide, substituted imidazolinide, benzimidazolide,or substituted benzimidazolide anions) may be depicted as follows:

wherein:

A*⁺ is a cation, especially a proton containing cation, and can betrihydrocarbyl ammonium cation containing one or two C₁₀₋₄₀ alkylgroups, especially a methyldi(C₁₄₋₂₀ alkyl)ammonium cation,

Q³, independently in each occurrence, is hydrogen or a halo,hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl,(including for example mono-, di- and tri(hydrocarbyl)silyl) group of upto 30 atoms not counting hydrogen, such as C₁₋₂₀ alkyl, and

Q² is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)alumane)

Examples of these catalyst activators includetrihydrocarbylammonium-salts, especially,methyldi(C_(i4-20)alkyl)ammonium-salts of:

bis(tris(pentafluorophenyl)borane)imidazolide,

bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide,

bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide,

bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide,

bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide,

bis(tris(pentafluorophenyl)borane)imidazolinide,

bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide,

bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide,

bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide,

bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolinide,

bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide,

bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide,

bis(tris(pentafluorophenyl)alumane)imidazolide,

bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide,

bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide,

bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolide,

bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide,

bis(tris(pentafluorophenyl)alumane)imidazolinide,

bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,

bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolinide,

bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide,

bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide,

bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide, and

bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.

Other activators include those described in the PCT publication WO98/07515, such as tris(2,2′,2″-nonafluorobiphenyl)fluoroaluminate.Combinations of activators are also contemplated by the disclosure, forexample, alumoxanes and ionizing activators in combinations, see forexample, EP-A-0 573120, PCT publications WO 94/07928 and WO 95/14044,and U.S. Pat. Nos. 5,153,157 and 5,453,410. For example, and in generalterms, WO 98/09996 describes activating catalyst compounds withperchlorates, periodates and iodates, including their hydrates. WO99/18135 describes the use of organoboroaluminum activators. WO 03/10171discloses catalyst activators that are adducts of Brønsted acids withLewis acids. Other activators or methods for activating a catalystcompound are described in, for example, U.S. Pat. Nos. 5,849,852,5,859,653, and 5,869,723, in EP-A-615981, and in PCT publication WO98/32775. All of the foregoing catalyst activators as well as any otherknown activator for transition metal complex catalysts may be employedalone or in combination according to the present disclosure. In oneaspect, however, the co-catalyst can be alumoxane-free. In anotheraspect, for example, the co-catalyst can be free of anyspecifically-named activator or class of activators as disclosed herein.

In a further aspect, the molar ratio of catalyst/co-catalyst employedgenerally ranges from 1:10,000 to 100:1, for example, from 1:5000 to10:1, or from 1:1000 to 1:1. Alumoxane, when used by itself as anactivating co-catalyst, can be employed in large quantity, generally atleast 100 times the quantity of metal complex on a molar basis.

Tris(pentafluorophenyl)borane, where used as an activating co-catalystcan be employed generally in a molar ratio to the metal complex of from0.5:1 to 10:1, such as from 1:1 to 6:1 and from 1:1 to 5:1. Theremaining activating co-catalysts are generally employed inapproximately equimolar quantity with the metal complex.

In exemplary embodiments of the present disclosure, the co-catalyst is[(C₁₆₋₁₈H₃₃₋₃₇)₂CH₃NH] tetrakis(pentafluorophenyl)borate salt.

Polymerization Process

The compositions of the present disclosure and catalyst systems usingthe compositions described herein are suitable for use in anyprepolymerization and/or polymerization process over a wide range oftemperatures and pressures. Such temperatures and pressures, as well asother polymerization process information, described herein can bereferred to as “polymerization conditions.” The temperatures may be inthe range of from −60° C. to about 280° C., preferably from 50° C. toabout 200° C. In another embodiment, the polymerization temperature isabove 0° C., above 50° C., above 80° C., above 100° C., above 150° C. orabove 200° C. In an embodiment, the pressures employed may be in therange from 1 atmosphere to about 500 atmospheres or higher.Polymerization processes include solution, gas phase, slurry phase and ahigh pressure process or a combination thereof.

In one embodiment, the process of the present disclosure is directedtoward a solution, high pressure, slurry or gas phase polymerizationprocess of one or more olefin monomers having from 2 to 30 carbon atoms,preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbonatoms. The present disclosure is particularly well suited to thepolymerization of two or more olefin monomers of ethylene, propylene,butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1 anddecene-1. Other monomers useful in the process of the present disclosureinclude ethylenically unsaturated monomers, diolefins having 4 to 18carbon atoms, conjugated or nonconjugated dienes, polyenes, vinylmonomers and cyclic olefins. Non-limiting monomers useful in the presentdisclosure may include norbornene, norbornadiene, isobutylene, isoprene,vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidenenorbornene, dicyclopentadiene and cyclopentene. In another embodiment ofthe process of the present disclosure, a copolymer of ethylene isproduced, where with ethylene, a comonomer having at least onealpha-olefin having from 4 to 15 carbon atoms, preferably from 4 to 12carbon atoms, and most preferably from 4 to 8 carbon atoms, ispolymerized in a solution process. In another embodiment of the processof the present disclosure, ethylene or propylene is polymerized with atleast two different comonomers, optionally one of which may be a diene,to form a terpolymer.

In embodiments of the process of this present disclosure, the catalystsystem may be employed in liquid phase (solution, slurry, suspension,bulk phase or combinations thereof), in high pressure liquid, orsupercritical fluid or gas phase processes. Each of these processes maybe employed in single, parallel or series reactors. The liquid processescomprise contacting the ethylene and/or cc-olefin and at least onevicinally disubstituted olefin monomer with the catalyst systemdescribed herein in a suitable diluent or solvent and allowing themonomers to react for a sufficient time to produce embodiments of theinvention copolymers. One or more of the monomers used in thepolymerization may be utilized as a solvent and/or diluent, generally inhomogeneous polymerizations in the liquid monomer or monomers.Hydrocarbyl solvents are also suitable, both aliphatic and aromatic,including hexane and toluene. Bulk and slurry processes may typically beaccomplished by contacting the catalysts with a slurry of liquidmonomer, the catalyst system being supported. Gas phase processes mayuse the supported catalyst and may be conducted in any manner known tobe suitable for producing ethylene homopolymers or copolymers viacoordination polymerization. Illustrative examples may be found in U.S.Pat. No. 4,543,399; 4,588,790; 5,028,670; 5,382,638; 5,352,749;5,436,304; 5,453,471; 5,463,999; and WO 95/07942. Each is incorporatedby reference for purposes of U.S. patent practice.

Generally, the polymerization reaction temperature may vary from −50° C.to 250° C. The reaction temperature conditions may be from −20° C. to220°, or below 200° C. The pressure may vary from 1 mm Hg to 2500 bar,or from 0.1 bar to 1600 bar, or from 1.0 to 500 bar. Where lowermolecular weight copolymers, e.g., M_(n)<10,000, are sought, it may besuitable to conduct the reaction processes at temperatures above 0° C.and pressures under 500 bar.

In one aspect of this disclosure, there is provided a process and theresulting polymer, the process comprising polymerizing one or moreolefin monomers in the presence of an olefin polymerization catalyst andthe composition having the formula (I) in a polymerization reactor orzone thereby causing the formation of at least some quantity of apolymer joined with the remnant of the composition having the formula(I). Exemplary, non-limiting polymerization processes include thoseknown in the art, those disclosed in U.S. Pat. No. 8,501,885 B2, as wellas those known in the art for producing random copolymers. Exemplary,non-limiting polymerization processes include those conducted in asingle reactor or two reactors.

In yet another aspect, there is provided a process and the resultingpolymer, the process comprising polymerizing one or more olefin monomersin the presence of an olefin polymerization catalyst and the compositionhaving the formula (I) in a polymerization reactor or zone therebycausing the formation of at least some quantity of an initial polymerjoined with the remnant of the composition having the formula (I) withinthe reactor or zone; discharging the reaction product from the firstreactor or zone to a second polymerization reactor or zone operatingunder polymerization conditions that are distinguishable from those ofthe first polymerization reactor or zone; transferring at least some ofthe initial polymer joined with the remnant of the composition havingthe formula (I) to an active catalyst site in the second polymerizationreactor or zone by means of at least one remaining shuttling site of thecomposition having the formula (I); and conducting polymerization in thesecond polymerization reactor or zone so as to form a second polymersegment bonded to some or all of the initial polymer by means of aremnant of the composition having the formula (I), the second polymersegment having distinguishable polymer properties from the initialpolymer segment.

During the polymerization, the reaction mixture is contacted with theactivated catalyst composition according to any suitable polymerizationconditions. The process can be generally characterized by use ofelevated temperatures and pressures. Hydrogen may be employed as a chaintransfer agent for molecular weight control according to knowntechniques, if desired. As in other similar polymerizations, it isgenerally desirable that the monomers and solvents employed be ofsufficiently high purity that catalyst deactivation or premature chaintermination does not occur. Any suitable technique for monomerpurification such as devolatilization at reduced pressure, contactingwith molecular sieves or high surface area alumina, or a combination ofthe foregoing processes may be employed.

Supports may be employed in the present methods, especially in slurry orgas-phase polymerizations. Suitable supports include solid,particulated, high surface area, metal oxides, metalloid oxides, ormixtures thereof (interchangeably referred to herein as an inorganicoxide). Examples include, but are not limited to talc, silica, alumina,magnesia, titania, zirconia, Sn₂O₃, aluminosilicates, borosilicates,clays, and any combination or mixture thereof. Suitable supportspreferably have a surface area as determined by nitrogen porosimetryusing the B. E. T. method from 10 to 1000 m²/g, and preferably from 100to 600 m²/g. The average particle size typically is from 0.1 to 500 μm,preferably from 1 to 200 μm, more preferably 10 to 100 μm.

In one aspect of the present disclosure, the catalyst composition andoptional support may be spray dried or otherwise recovered in solid,particulated form to provide a composition that is readily transportedand handled. Suitable methods for spray drying a liquid containingslurry are well known in the art and usefully employed herein. Preferredtechniques for spray drying catalyst compositions for use herein aredescribed in U.S. Pat. Nos. 5,648,310 and 5,672,669.

The polymerization is desirably carried out as a continuouspolymerization, for example, a continuous, solution polymerization, inwhich catalyst components, monomers, and optionally solvent, adjuvants,scavengers, and polymerization aids are continuously supplied to one ormore reactors or zones and polymer product continuously removedtherefrom. Within the scope of the terms “continuous” and “continuously”as used in this context include those processes in which there areintermittent additions of reactants and removal of products at smallregular or irregular intervals, so that, over time, the overall processis substantially continuous. The composition having the formula (I) (ifused) may be added at any point during the polymerization including inthe first reactor or zone, at the exit or slightly before the exit ofthe first reactor, between the first reactor or zone and any subsequentreactor or zone, or even solely to the second reactor or zone. If thereexists any difference in monomers, temperatures, pressures or otherpolymerization conditions within a reactor or between two or morereactors or zones connected in series, polymer segments of differingcomposition such as comonomer content, crystallinity, density,tacticity, regio-regularity, or other chemical or physical differences,within the same molecule can be formed in the polymers of thisdisclosure. In such event, the size of each segment or block isdetermined by the polymer reaction conditions and typically is a mostprobable distribution of polymer sizes.

If multiple reactors are employed, each can be independently operatedunder high pressure, solution, slurry, or gas phase polymerizationconditions. In a multiple zone polymerization, all zones operate underthe same type of polymerization, such as solution, slurry, or gas phase,but, optionally, at different process conditions. For a solutionpolymerization process, it is desirable to employ homogeneousdispersions of the catalyst components in a liquid diluent in which thepolymer is soluble under the polymerization conditions employed. Onesuch process utilizing an extremely fine silica or similar dispersingagent to produce such a homogeneous catalyst dispersion wherein normallyeither the metal complex or the co-catalyst is only poorly soluble isdisclosed in U.S. Pat. No. 5,783,512. A high pressure process is usuallycarried out at temperatures from 100° C. to 400° C. and at pressuresabove 500 bar (50 MPa). A slurry process typically uses an inerthydrocarbon diluent and temperatures of from 0° C. up to a temperaturejust below the temperature at which the resulting polymer becomessubstantially soluble in the inert polymerization medium. For example,typical temperatures in a slurry polymerization are from 30° C.,generally from 60° C. up to 115° C., including up to 100° C., dependingon the polymer being prepared. Pressures typically range fromatmospheric (100 kPa) to 500 psi (3.4 MPa).

In all of the foregoing processes, continuous or substantiallycontinuous polymerization conditions generally are employed. The use ofsuch polymerization conditions, especially continuous, solutionpolymerization processes, allows the use of elevated reactortemperatures which results in the economical production of the presentblock copolymers in high yields and efficiencies.

The catalyst may be prepared as a homogeneous composition by addition ofthe requisite metal complex or multiple complexes to a solvent in whichthe polymerization will be conducted or in a diluent compatible with theultimate reaction mixture. The desired co-catalyst or activator and,optionally, a composition having the formula (I) may be combined withthe catalyst composition either prior to, simultaneously with, or aftercombination of the catalyst with the monomers to be polymerized and anyadditional reaction diluent. Desirably, if present, the compositionhaving the formula (I) is added at the same time.

At all times, the individual ingredients as well as any active catalystcomposition are protected from oxygen, moisture, and other catalystpoisons. Therefore, the catalyst components, the composition having theformula (I), and activated catalysts are prepared and stored in anoxygen and moisture free atmosphere, generally under a dry, inert gassuch as nitrogen.

Without limiting in any way the scope of the disclosure, one means forcarrying out such a polymerization process is as follows. In one or morewell stirred tank or loop reactors operating under solutionpolymerization conditions, the monomers to be polymerized are introducedcontinuously together with any solvent or diluent at one part of thereactor. The reactor contains a relatively homogeneous liquid phasecomposed substantially of monomers together with any solvent or diluentand dissolved polymer. Preferred solvents include C₄₋₁₀ hydrocarbons ormixtures thereof, especially alkanes such as hexane or mixtures ofalkanes, as well as one or more of the monomers employed in thepolymerization. Examples of suitable loop reactors and a variety ofsuitable operating conditions for use therewith, including the use ofmultiple loop reactors, operating in series, are found in U.S. Pat. Nos.5,977,251, 6,319,989 and 6,683,149.

Catalyst along with co-catalyst and the composition having the formula(I) are continuously or intermittently introduced in the reactor liquidphase or any recycled portion thereof at a minimum of one location. Thereactor temperature and pressure may be controlled, for example, byadjusting the solvent/monomer ratio or the catalyst addition rate, aswell as by use of cooling or heating coils, jackets or both. Thepolymerization rate can be controlled by the rate of catalyst addition.The content of a given monomer in the polymer product is influenced bythe ratio of monomers in the reactor, which is controlled bymanipulating the respective feed rates of these components to thereactor. The polymer product molecular weight is controlled, optionally,by controlling other polymerization variables such as the temperature,monomer concentration, or by the previously mentioned composition havingthe formula (I), or a chain terminating agent such as hydrogen, as isknown in the art.

In one aspect of the disclosure, a second reactor is connected to thedischarge of a first reactor, optionally by means of a conduit or othertransfer means, such that the reaction mixture prepared in the firstreactor is discharged to the second reactor without substantialtermination of polymer growth. Between the first and second reactors, adifferential in at least one process condition may be established.Generally, for use in formation of a copolymer of two or more monomers,the difference is the presence or absence of one or more comonomers or adifference in comonomer concentration. Additional reactors, eacharranged in a manner similar to the second reactor in the series may beprovided as well. Further polymerization is ended by contacting thereactor effluent with a catalyst kill agent such as water, steam or analcohol or with a coupling agent if a coupled reaction product isdesired.

The resulting polymer product is recovered by flashing off volatilecomponents of the reaction mixture such as residual monomer(s) ordiluent at reduced pressure, and, if necessary, conducting furtherdevolatilization in equipment such as a devolatilizing extruder. In acontinuous process the mean residence time of the catalyst and polymerin the reactor generally is from 5 minutes to 8 hours, for example, from10 minutes to 6 hours.

In a further aspect of this disclosure, alternatively, the foregoingpolymerization may be carried out in a plug flow reactor optionally witha monomer, catalyst, the composition having the formula (I), temperatureor other gradient established between differing zones or regionsthereof, further optionally accompanied by separate addition ofcatalysts and/or the composition having the formula (I), and operatingunder adiabatic or non-adiabatic polymerization conditions.

In yet a further aspect, the catalyst composition may also be preparedand employed as a heterogeneous catalyst by adsorbing the requisitecomponents on an inert inorganic or organic particulated solid, aspreviously disclosed. For example, a heterogeneous catalyst can beprepared by co-precipitating the metal complex and the reaction productof an inert inorganic compound and an active hydrogen containingactivator, especially the reaction product of a tri(C₁₋₄ alkyl) aluminumcompound and an ammonium salt of ahydroxyaryltris(pentafluorophenyl)borate, such as an ammonium salt of(4-hydroxy-3,5-ditertiarybutylphenyl)tris(pentafluorophenyl)borate. Whenprepared in heterogeneous or supported form, the catalyst compositionmay be employed in a slurry or a gas phase polymerization. As apractical limitation, slurry polymerization takes place in liquiddiluents in which the polymer product is substantially insoluble.Generally, the diluent for slurry polymerization is one or morehydrocarbons with less than 5 carbon atoms. If desired, saturatedhydrocarbons such as ethane, propane, or butane may be used in whole orpart as the diluent. As with a solution polymerization, the α-olefincomonomer or a combination of different α-olefin monomers may be used inwhole or part as the diluent. Most preferably at least a major part ofthe diluent comprises the α-olefin monomer or monomers to bepolymerized.

In this aspect, for use in gas phase polymerization processes, thesupport material and resulting catalyst typically can have a medianparticle diameter from 20 to 200 μm, generally from 30 μm to 150 μm, andtypically from 50 μm to 100 μm. For use in slurry polymerizationprocesses, the support can have a median particle diameter from 1 μm to200 μm, generally from 5 μm to 100 μm, and typically from 10 μm to 80μm.

Suitable gas phase polymerization process for use herein aresubstantially similar to known processes used commercially on a largescale for the manufacture of polypropylene, ethylene/α-olefincopolymers, and other olefin polymers. The gas phase process employedcan be, for example, of the type which employs a mechanically stirredbed or a gas fluidized bed as the polymerization reaction zone.Preferred is the process wherein the polymerization reaction is carriedout in a vertical cylindrical polymerization reactor containing afluidized bed of polymer particles supported or suspended above aperforated plate or fluidization grid, by a flow of fluidization gas.Suitable gas phase processes which are adaptable for use in the processof this disclosure are disclosed in, for example, U.S. Pat. Nos.4,588,790; 4,543,399; 5,352,749; 5,436,304; 5,405,922; 5,462,999;5,461,123; 5,453,471; 5,032,562; 5,028,670; 5,473,028; 5,106,804;5,556,238; 5,541,270; 5,608,019; and 5,616,661.

The use of functionalized derivatives of polymers are also includedwithin the present disclosure. Examples include metallated polymerswherein the metal is the remnant of the catalyst or the compositionhaving the formula (I) employed, as well as further derivatives thereof.Because a substantial fraction of the polymeric product exiting thereactor is terminated with metal, further functionalization isrelatively easy. The metallated polymer species can be utilized in wellknown chemical reactions such as those suitable for otheralkyl-aluminum, alkyl-gallium, alkyl-zinc, or alkyl-Group 1 compounds toform amine-, hydroxy-, epoxy-, silane, vinylic, and other functionalizedterminated polymer products. Examples of suitable reaction techniquesthat are adaptable for use herein are described in Negishi,“Organometallics in Organic Synthesis”, Vol. 1 and 2, (1980), and otherstandard texts in organometallic and organic synthesis.

Olefin Monomers

Suitable monomers for use in preparing the polymer products of thepresent disclosure in polymerization processes include any additionpolymerizable monomer, generally any olefin or diolefin monomer.Suitable monomers can be linear, branched, acyclic, cyclic, substituted,or unsubstituted. In one aspect, the olefin can be any α-olefin,including, for example, ethylene and at least one differentcopolymerizable comonomer, propylene and at least one differentcopolymerizable comonomer having from 4 to 20 carbons, or4-methyl-1-pentene and at least one different copolymerizable comonomerhaving from 4 to 20 carbons. Examples of suitable monomers include, butare not limited to, straight-chain or branched a-olefins having from 2to 30 carbon atoms, from 2 to 20 carbon atoms, or from 2 to 12 carbonatoms. Specific examples of suitable monomers include, but are notlimited to, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene,1-hexane, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.Suitable monomers for use in preparing the copolymers disclosed hereinalso include cycloolefins having from 3 to 30, from 3 to 20 carbonatoms, or from 3 to 12 carbon atoms. Examples of cycloolefins that canbe used include, but are not limited to, cyclopentene, cycloheptene,norbornene, 5-methyl-2-norbornene, tetracyclododecene, and2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.Suitable monomers for preparing the copolymers disclosed herein alsoinclude di- and poly-olefins having from 3 to 30, from 3 to 20 carbonatoms, or from 3 to 12 carbon atoms. Examples of di- and poly-olefinsthat can be used include, but are not limited to, butadiene, isoprene,4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene,1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene,1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene,vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene,4-ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decatriene.In a further aspect, aromatic vinyl compounds also constitute suitablemonomers for preparing the copolymers disclosed here, examples of whichinclude, but are not limited to, mono- or poly-alkylstyrenes (includingstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene),and functional group-containing derivatives, such as methoxystyrene,ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzylacetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene,divinylbenzene, 3-phenylpropene, 4-phenylpropene and α-methylstyrene,vinylchloride, 1,2-difluoroethylene, 1,2-dichloroethylene,tetrafluoroethylene, and 3,3,3-trifluoro-1-propene, provided the monomeris polymerizable under the conditions employed.

Further, in one aspect, suitable monomers or mixtures of monomers foruse in combination with the composition having the formula (I) or (II)disclosed here include ethylene; propylene; mixtures of ethylene withone or more monomers selected from propylene, 1-butene, 1-hexene,4-methyl-1-pentene, 1-octene, and styrene; and mixtures of ethylene,propylene and a conjugated or non-conjugated diene. In this aspect, thecopolymer or interpolymer can contain two or more intramolecular regionscomprising differing chemical or physical properties, especially regionsof differentiated comonomer incorporation, joined in a dimeric, linear,branched or polybranched polymer structure. Such polymers may beprepared by altering the polymerization conditions during apolymerization that includes a composition having the formula (I) or(II), for example by using two reactors with differing comonomer ratios,multiple catalysts with differing comonomer incorporation abilities, ora combination of such process conditions, and optionally apolyfunctional coupling agent.

Polymer Products

As disclosed herein, the polymer products refer to polymer products,after polymerization, that are typically subjected to chemical treatmentto consume reactive metal alkyl groups and liberate the polymer productsfrom attachment to transition group or main group metals. This processcomprises hydrolysis with water to generate saturated polymer endgroups. Alternatively, addition of various organic or inorganic reagentsmay be added to both consume the metal alkyl groups and generatereactive functional end groups on the polymer chains.

The polymers produced by the processes of the present disclosure can beused in a wide variety of products and end-use applications. Thepolymers produced can be homo- and co-polymers of ethylene and propyleneand include linear low density polyethylene, elastomers, plastomers,high-density polyethylenes, medium density polyethylenes, low densitypolyethylenes, polypropylene, and polypropylene copolymers. Propylenebased polymers produced include isotactic polypropylene, atacticpolypropylene, and random, block or impact copolymers.

Utilizing the polymerization processes disclosed here, novel polymercompositions, including block copolymers of one or more olefin monomershaving the present molecular weight distribution, are readily prepared.Exemplary polymers comprise in polymerized form at least one monomerselected from ethylene, propylene, and 4-methyl-1-pentene.Illustratively, the polymers are interpolymers comprising in polymerizedform ethylene, propylene, or 4-methyl-1-pentene and at least onedifferent C₂₋₂₀ α-olefin comonomer, and optionally one or moreadditional copolymerizable comonomers. Suitable comonomers are selectedfrom diolefins, cyclic olefins, and cyclic diolefins, halogenated vinylcompounds, vinylidene aromatic compounds, and combinations thereof.Exemplary polymers are interpolymers of ethylene with propylene,1-butene, 1-hexene or 1-octene. Illustratively, the polymer compositionsdisclosed here have an ethylene content from 1 to 99 percent, a dienecontent from 0 to 10 percent, and a styrene and/or C₃₋₈ α-olefin contentfrom 99 to 1 percent, based on the total weight of the polymer. Thepolymers of the present disclosure may have a weight average molecularweight (Mw) from 10,000 to 2,500,000. Typically, the polymers of thepresent disclosure have a weight average molecular weight (Mw) from 500to 250,000 (e.g., from 2,000 to 150,000, from 3,000 to 100,000, from1,000 to 25,000, from 5,000 to 25,000, etc.).

The polymers prepared according to this disclosure can have a meltindex, 12, from 0.01 to 2000 g/10 minutes, typically from 0.01 to 1000g/10 minutes, more typically from 0.01 to 500 g/10 minutes, andespecially from 0.01 to 100 g/10 minutes. Desirably, the disclosedpolymers can have molecular weights, M_(w), from 1,000 g/mole to5,000,000 g/mole, typically from 1000 g/mole to 1,000,000, moretypically from 1000 g/mole to 500,000 g/mole, and especially from 1,000g/mole to 300,000 g/mole.

The density of the polymers of this disclosure can be from 0.80 to 0.99g/cm³ and typically, for ethylene containing polymers, from 0.85 g/cm³to 0.97 g/cm³ (e.g., from 0.853 to 0.970 g/cm³).

The polymers according to this disclosure may be differentiated fromconventional, random copolymers, physical blends of polymers, and blockcopolymers prepared via sequential monomer addition, fluxionalcatalysts, or by anionic or cationic living polymerization techniques,by, among other things, their narrow molecular weight distributions. Inthis aspect, for example, the polymer composition prepared according tothis disclosure can be characterized by a polydispersity index (PDI) offrom 1.5 to 10.0 (e.g, from 2.0 to 8.0, from 2.0 to 6.0, from 2.0 to5.0, from 2.0 to 4.0, etc.). For example, the polydispersity index (PDI)of the polymer composition can be from 1.5 to 2.8, from 1.5 to 2.5, orfrom 1.5 to 2.3.

If present, the separate regions or blocks within each polymer arerelatively uniform, depending on the uniformity of reactor conditions,and chemically distinct from each other. That is, the comonomerdistribution, tacticity, or other property of segments within thepolymer are relatively uniform within the same block or segment.However, the average block length can be a narrow distribution, but isnot necessarily so. The average block length can also be a most probabledistribution.

Illustratively, these interpolymers can be characterized by terminalblocks or segments of polymer having higher tacticity or crystallinityfrom at least some remaining blocks or segments. Illustratively, thepolymer can be a triblock copolymer containing a central polymer blockor segment that is relatively amorphous or even elastomeric.

In a still further aspect of this disclosure, there is provided apolymer composition comprising: (1) an organic or inorganic polymer,preferably a homopolymer of ethylene or of propylene and/or a copolymerof ethylene or propylene with one or more copolymerizable comonomers,and (2) a polymer or combination of polymers according to the presentdisclosure or prepared according to the process disclosed here.

The inventive polymer products include combinations of two or morepolymers comprising regions or segments (blocks) of differing chemicalcomposition. In addition, at least one of the constituents of thepolymer combination can contain a linking group which is the remnant ofthe composition having the formula (I), causing the polymer to possesscertain physical properties.

Various additives may be usefully incorporated into the presentcompositions in amounts that do not detract from the properties of theresultant composition. These additives include, for example, reinforcingagents, fillers including conductive and non-conductive materials,ignition resistant additives, antioxidants, heat and light stabilizers,colorants, extenders, crosslinkers, blowing agents, plasticizers, flameretardants, anti-drip agents, lubricants, slip additives, anti-blockingaids, anti-degradants, softeners, waxes, pigments, and the like,including combinations thereof.

The resultant polymers may be block interpolymers that can becharacterized by an average block index, e.g., as discussed in U.S. Pat.Nos. 7,947,793, 7,897,698, and 8,293,859. The resultant polymers may beblock composites that can be characterized by a block composite index,e.g., as discussed in U.S. Pat. Nos. 8,563,658, 8,476,366, 8,686,087,and 8,716,400. The resultant polymers may be crystalline blockcomposites that can be characterized by a crystalline block compositeindex, e.g., as discussed in U.S. Pat. Nos. 8,785,554, 8,822,598, and8,822,599. The resultant polymers may be specified block composites thatcan be characterized by a microstructure index, e.g., as discussed in WO2016/028957. The resultant polymers may be specified block compositesthat can be characterized by a modified block composite index, e.g., asdiscussed in WO 2016/028970.

In certain embodiments, the process for preparing the composition havingthe formula (I) may be combined with functionalization chemistry todevelop telechelic olefin prepolymers. In certain embodiments, thecomposition having the formula (I) can generate and grow telechelicpolymer chains with both ends bonded to the composition having theformula (I); subsequent transformation of the terminal polymeryl-metalbonds to desired di-end-functional groups may then occur to form thetelechelic polymer.

Applications of the combination of the process for preparing thecomposition having the formula (I) of the present disclosure withfunctionalization chemistry are in no way limited to development oftelechelic olefin prepolymers and the above example. In certainembodiments, the process for preparing the composition having theformula (I) of the present disclosure may be combined with, e.g.,coordinative chain transfer polymerization, to produce functionalizedpolyolefins.

The polymers of the present disclosure may be blended and/or coextrudedwith any other polymer. Non-limiting examples of other polymers includelinear low density polyethylenes, elastomers, plastomers, high pressurelow density polyethylene, high density polyethylenes, isotacticpolypropylene, ethylene propylene copolymers and the like.

Polymers produced by the process of the present disclosure and blendsthereof are useful in such forming operations as film, sheet, and fiberextrusion and co-extrusion as well as blow molding, injection molding,roto-molding Films include blown or cast films formed by coextrusion orby lamination useful as shrink film, cling film, stretch film, sealingfilm or oriented films.

EXAMPLES Methodologies

¹H NMR: ¹H NMR spectra are recorded on a Bruker AV-400 spectrometer atambient temperature. ¹H NMR chemical shifts in benzene-d₆ are referencedto 7.16 ppm (C₆D₅H) relative to TMS (0.00 ppm).

¹³C NMR: ¹³C NMR spectra of polymers are collected using a Bruker 400MHz spectrometer equipped with a Bruker Dual DUL high-temperatureCryoProbe. The polymer samples are prepared by adding approximately 2.6gof a 50/50 mixture of tetrachloroethane-d₂/orthodichlorobenzenecontaining 0.025M chromium trisacetylacetonate (relaxation agent) to 0.2g of polymer in a 10 mm NMR tube. The samples are dissolved andhomogenized by heating the tube and its contents to 150° C. The data isacquired using 320 scans per data file, with a 7.3 second pulserepetition delay with a sample temperature of 120° C.

GCMS: Tandem gas chromatography/low resolution mass spectroscopy usingelectron impact ionization (EI) is performed at 70 eV on an AgilentTechnologies 6890N series gas chromatograph equipped with an AgilentTechnologies 5975 inert XL mass selective detector and an AgilentTechnologies Capillary column (HP1MS, 15 m×0.25mm, 0 25 micron) withrespect to the following:

Programed method:

Oven Equilibration Time 0.5 min

50° C. for 0 min

then 25° C./min to 200° C. for 5 min

Run Time 11 min

DSC Standard Method: Differential Scanning calorimetry results aredetermined using a TAI model Q1000 DSC equipped with an RCS coolingaccessory and an autosampler. A nitrogen purge gas flow of 50 ml/min isused. The sample is pressed into a thin film and melted in the press at175° C. and then air-cooled to room temperature (25° C.). About 10 mg ofmaterial in the form of a 5-6 mm diameter disk is accurately weighed andplaced in an aluminum foil pan (ca 50 mg) which is then crimped shut.The thermal behavior of the sample is investigated with the followingtemperature profile. The sample is rapidly heated to 180° C. and heldisothermal for 3 minutes in order to remove any previous thermalhistory. The sample is then cooled to −40° C. at 10° C./min cooling rateand held at −40° C. for 3 minutes. The sample is then heated to 150° C.at 10° C./min heating rate. The cooling and second heating curves arerecorded.

The DSC melting peak is measured as the maximum in heat flow rate (W/g)with respect to the linear baseline drawn between −30° C. and end ofmelting. The heat of fusion is measured as the area under the meltingcurve between −30° C. and the end of melting using a linear baseline.

Molecular Weight Determination: Molecular weights are determined byoptical analysis techniques including deconvoluted gel permeationchromatography coupled with a low angle laser light scattering detector(GPC-LALLS) as described by Rudin, A., “Modern Methods of PolymerCharacterization”, John Wiley & Sons, New York (1991) pp. 103-112.

GPC Method: The gel permeation chromatographic system consists of eithera Polymer Laboratories Model PL-210 or a Polymer Laboratories ModelPL-220 instrument. The column and carousel compartments are operated at140° C. Three Polymer Laboratories 10-micron Mixed-B columns are used.The solvent is 1,2,4 trichlorobenzene. The samples are prepared at aconcentration of 0.1 grams of polymer in 50 milliliters of solventcontaining 200 ppm of butylated hydroxytoluene (BHT). Samples areprepared by agitating lightly for 2 hours at 160° C. The injectionvolume used is 100 microliters and the flow rate is 1.0 ml/minute.

Calibration of the GPC column set is performed with 21 narrow molecularweight distribution polystyrene standards with molecular weights rangingfrom 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least adecade of separation between individual molecular weights. The standardsare purchased from Polymer Laboratories (Shropshire, UK). Thepolystyrene standards are prepared at 0.025 grams in 50 milliliters ofsolvent for molecular weights equal to or greater than 1,000,000 and0.05 grams in 50 milliliters of solvent for molecular weights less than1,000,000. The polystyrene standards are dissolved at 80° C. with gentleagitation for 30 minutes. The narrow standards mixtures are run firstand in order of decreasing highest molecular weight component tominimize degradation. The polystyrene standard peak molecular weightsare converted to polyethylene molecular weights using the followingequation (as described in Williams and Ward, J. Polym. ScL, Polym. Let.,6, 621 (1968)):

M_(po)i_(yethy)i_(ene)=0.43 l(M_(po)i_(ystyrene)). Polyethyleneequivalent molecular weight calculations are performed using ViscotekTriSEC software Version 3.0.

Density: Density measurements are conducted according to ASTM D792.

Mooney viscosity: Mooney Viscosity (ML1+4 at 125° C.) is measured inaccordance with ASTM 1646, with a one minute preheat time and a fourminute rotor operation time. The instrument is an Alpha TechnologiesMooney Viscometer 2000.

Melt viscosity (Brookfield viscosity): Melt viscosity is measured inaccordance with ASTM D 3236 (177° C., 350° F.), using a BrookfieldDigital Viscometer (Model DV-III, version 3), and disposable aluminumsample chambers. The spindle is a SC-31 hot-melt spindle, suitable formeasuring viscosities in the range from 10 to 100,000 centipoise. Thesample is poured into the chamber, which is, in turn, inserted into aBrookfield Thermosel, and locked into place. The sample chamber has anotch on the bottom that fits the bottom of the Brookfield Thermosel, toensure that the chamber is not allowed to turn when the spindle isinserted and spinning The sample (approximately 8-10 grams of resin) isheated to the required temperature, until the melted sample is about oneinch below the top of the sample chamber. The viscometer apparatus islowered, and the spindle submerged into the sample chamber. Lowering iscontinued, until the brackets on the viscometer align on the Thermosel.The viscometer is turned on, and set to operate at a shear rate whichleads to a torque reading in the range of 40 to 60 percent of the totaltorque capacity, based on the rpm output of the viscometer. Readings aretaken every minute for about 15 minutes, or until the values stabilize,at which point, a final reading is recorded.

Zn content in polymer: The zinc content is measured by XRF analysisusing the PANalytical 2400 wavelength dispersive X-ray spectrometerunder helium atmosphere. A channel mask of 24 mm is used. The countingtimes for peak and background are 30 s. The AUSMON-He monitor is used tocorrect for any drift over time. The polymer samples are hot pressedinto plaques using a Leco PR-32 mounting press at a constant temperatureof 150° C. and pressure of about 4000 psi. Ten grams of polymer are usedto mold a plaque with a diameter of 31 mm.

P wt %: The propylene content is measured by ¹³C NMR, described above.

Materials

The following materials are principally used in the examples of thepresent disclosure.

Anhydrous toluene is obtained from Sigma-Aldrich and is further driedover alumina, which is activated in a 275° C. oven for about 5 hours.1,2,4-trivinylcyclohexane (“TVCH”) is obtained from Sigma-Aldrich and isdried over activated alumina before use. Diethylzinc (“DEZ” or “ZnEt2”)and triethylaluminum (“TEA” or “AlEt3”) are obtained from Sigma-Aldrich.[(C₁₆₋₁₈H₃₃₋₃₇)₂CH₃NH] tetrakis(pentafluorophenyl)borate salt(“Co-catalyst A”) is obtained from Boulder Scientific Co. Isopar™ E isobtained from Exxon. MMAO-3A is obtained from Akzo.5-ethylidene-2-norbornene (“ENB,” mixture of endo and exo) is obtainedfrom Sigma-Aldrich and dried over DD6 before use. 1,9-decadiene isobtained from Sigma-Aldrich. Silica ES757-875 is obtained from INEOSSilicas and is dehydrated at high temperature (about 700-800° C.).Norbornene (“NBN”) is obtained from Sigma-Aldrich.

(E)-((2,6-diisopropylphenyl)(2-methyl-3-(octylimino)butan-2-yl)amino)trimethylhafnium (“Catalyst (A2)”) is obtained from Boulder Scientific Co. andprepared according to methods known in the art. The structure ofCatalyst (A2) is illustrated below:

The following examples are provided as further illustrations of thepresent disclosure and are not to be construed as limiting. The term“overnight”, if used, refers to a time of approximately 16-18 hours, andthe term “room temperature” refers to a temperature of 20-25° C. In theevent the name of a compound herein does not conform to the structuralrepresentation thereof, the structural representation shall control. Thesynthesis of all metal complexes and the preparation of all screeningexperiments are carried out in a dry nitrogen atmosphere using dry box(glove box) techniques, including running reactions entirely within adry box under a nitrogen atmosphere. All solvents used are HPLC gradeand are dried before their use.

REFERENCE EXAMPLE

In a drybox under an atmosphere of nitrogen, TVCH (0.327 ml, 1.68 mmol),DEZ (0.2 ml, 1.94 mmol) and Co-catalyst A (0.06 mmol in 1 mlmethylcyclohexane) are added to 7 ml of toluene in a 2 oz glass vialequipped with a stir-bar. A sample is taken for ¹H NMR in C6D6, as seenin the “before reaction” spectrum in FIG. 1. Catalyst (A2) (19 mg in 2ml toluene, 0.032 mmol) is added to initiate the reaction and to form afirst solution containing the composition of the Reference Example. Thefirst solution is stirred at room temperature overnight and has a [Zn]of 0.22 M.

A sample of the first solution is diluted in benzene-d6 for “afterovernight reaction” ¹H NMR analysis as seen in FIG. 1. As seen in FIG.1, only trace amounts of vinyl unsaturation are left in the “afterovernight reaction” spectrum, indicating that the vinyl groups of TVCHare consumed after overnight reaction. Concurrently, the ZnEt peak isalso diminished, but a small amount remains as seen on the ¹H NMRspectra. Accordingly, ¹H NMR analysis provides proof of the coordinationand insertion of TVCH into the transition metal catalyst precursorfollowed by chain transfer to zinc.

Further samples of the first solution are also analyzed via GCMS. Morespecifically, as seen in FIGS. 3A and 3B, aliquots of the first solutionare quenched by water and deuterium oxide separately. As seen in FIGS.3A and 3B, the water quenched sample shows major peaks at m/z of about222, while the D2O quenched sample shows major peaks at m/z of about224; these peaks are consistent with the expected hydrolyzed productsshown below in exemplary, non-limiting Scheme 5. The multiplicity ofpeaks is believed to be the result of multiple chiral centers in thestructure.

Furthermore, GCMS analysis shows the surprising and unexpected nature ofthe present disclosure. It was hypothesized that TVCH might form athree-headed organometallic species since TVCH has three vinyl groups;such a three-headed organometallic species would generate a hydrolyzedproduct with a molecular weight of about 252, as illustrated below inexemplary, non-limiting Scheme 6. Surprisingly, GCMS does not detectpeaks at m/z of about 252. Instead, it unexpectedly shows groups ofpeaks at m/z of about 222, which is consistent with the double-ringstructures formed by intramolecular insertion of two neighboring vinylgroups. Accordingly, an exemplary mechanism is insertion of the firstvinyl group on the transition metal followed by the consecutiveinsertion of the neighboring vinyl in 2,1-fashion to form a 6/6 ringstructure or in 1,2-fashion to form a 6/5 ring structure as shown inexemplary, non-limiting Scheme 4. The minor peaks at m/z of about 192are presumably half reacted TVCH with only one vinyl group inserted.

The D2O quenched sample confirms the dual-headed nature of theorganometallic species. As anticipated, the 222 peaks on the GCMS shiftto about 224 for the D2O quenched sample, indicating that the alkanemoiety is attached to two zinc atoms before hydrolysis.

To further probe the structure, a further sample of the first solutionis hydrolyzed with deuterium oxide, and ¹³C NMR analysis is performed onthe isolated hydrolyzed product, as seen in FIG. 2. As seen in FIG. 2,¹³C NMR analysis shows that the isolated hydrolyzed product isconsistent with the structure shown in exemplary, non-limiting Scheme 5.Specifically, as seen in FIG. 2, the deuterium labelled carbons shiftslightly up-field and split into three peaks and are, thus, easilydistinguished from the unlabeled carbons. As indicated in exemplary,non-limiting Scheme 7, the 6/6 ring structure would have one labelledprimary carbon and one labelled secondary carbon (CH2D:CHD=1), and the6/5 ring structure would have two labelled primary carbons withdifferent chemical shift (CH2D(1):CH2D(2)=1). If the product is amixture of the two, we would get CH2D(1):[CH2D(2)+CHD]=1. As shown bythe ¹³C NMR spectra in FIG. 2, no CHD (D on secondary carbon) isdetected; there are two CH2D peaks with similar intensity. The resultindicates that the product has a 6/5 ring structure. It is noted thatthe D-labelling is not complete, possibly due to residual water in theD2O reagent.

Ethylene Polymerization with the Composition of the Reference Example:To validate the dual-headed composition of the Reference Example,ethylene polymerization is performed using the composition in apolymerization setup. ISOPAR™ E (10 ml), MMAO-3A (0.03 mmol) andCo-catalyst A (0.0013 mmol) are added to a 40 ml glass vial equippedwith a stirbar in the drybox. The vial is capped with a septum lined lidand connected to an ethylene line via a needle. Another needle isinserted on the lid to let ethylene slowly purge the vial for 2 min. Thevial is placed in a heating block at 100° C. The first solution of theReference Example (2 ml, 0.4 mmol) and Catalyst (A2) (0.001 mmol) areinjected, and the purge needle is removed to maintain a total pressureat 12 psig. The reaction is maintained for 30 min. After polymerization,0.5 ml of deuterated isopropyl alcohol (iPrOD) is added to quench thereaction. The mixture is moved out of the drybox and poured into a largeamount of MeOH. The precipitated polymer is filtered, dried under vacuumat RT overnight then at 70° C. for 3 hr. 0.5 g of white polyethylene isobtained. Such a procedure is cursorily illustrated below in exemplary,non-limiting Scheme 8.

As seen in FIG. 4, ¹³C NMR analysis of the polymer shows the ethylgroups from the composition fragment as well as the labeled and someunlabeled chain ends due to incomplete quenching. The result validatesthe effective transfer of polymer chains to the composition and chaingrowth in a dual headed fashion.

WORKING EXAMPLE 1

TVCH (0.19 ml, 0.97 mmol), DEZ (0.2 ml, 1.94 mmol) and Co-catalyst A(0.48 ml of 0.0644 M solution, 0.03 mmol) are added to toluene (7 ml) ina 20 ml glass vial under nitrogen atmosphere. A sample is taken for ¹HNMR in C6D6, as seen in the “before reaction” spectrum in FIG. 5.Catalyst (A2) (10 mg dissolved in 2 ml toluene, 0.02 mmol) is added andthe mixture is stirred at room temperature to form a first solution.After 2 hours, the reaction is completed as indicated by thedisappearance of the vinyl peaks on ¹H NMR as seen in the “2 h” spectrumof FIG. 5. The ZnEt peak is reduced but still present. ENB (0.234 g,1.94 mmol) is added and the mixture is stirred overnight to form a finalsolution containing the composition of Working Example 1. As seen in the“overnight” spectrum of FIG. 5, ¹HNMR shows all the remaining ZnEt andall the ENB are consumed. The final solution has a [Zn] of 0.22 M.Accordingly, ¹H NMR analysis shows that the synthesis reaction proceededas intended. All the remaining ZnEt is replaced by ENB. The process forpreparing the composition of Working Example 1 is illustrated below inexemplary, non-limiting Scheme 9.

The intended structure of the dual-headed composition of Working Example1 is confirmed via GCMS analysis. As seen in FIG. 6, GCMS of ahydrolyzed sample of the first solution confirms the formation of theexpected, uncapped TVCH-based composition at m/z=222 and the presence ofsome half converted TVCH. As seen in FIG. 7, GCMS of a hydrolyzed sampleof the final solution confirms the formation of the expected cappinggroup at m/z=150 and the core YY structure (i.e., the derivative of theTVCH linking group) at m/z=222. There are multiple small peaks at m/z of164-166, presumably belonging to the oxidized capping group due toincomplete hydrolysis. Accordingly, the GCMS results indicate that thedesired capped structure is obtained.

Ethylene Polymerization with the composition of Working Example 1: Tovalidate the dual-headed composition of Working Example 1, ethylenepolymerization is performed using the composition in a polymerizationsetup in a glovebox via the reactions illustrated in exemplary,non-limiting Scheme 10. ISOPAR™ E (10 ml) and Co-Catalyst A (0.0039mmol) are added to a 40 ml glass vial equipped with a stirbar in thedrybox. The vial is capped with a septum lined lid and connected to anethylene line via a needle. Another needle is inserted on the lid to letethylene slowly purge the vial for 2 min. The vial is placed in aheating block at 100° C. The final solution of Working Example 1 (2 ml,0.44 mmol) and Catalyst (A2) (0.003 mmol) are injected, and the purgeneedle is removed to maintain a total pressure at 10 psig. The reactionis maintained for 30 min. After polymerization, 0.5 ml of deuteratedmethanol (MeOD) is added to quench the reaction. The mixture is movedout of the drybox and poured into a large amount of MeOH. Theprecipitated polymer is filtered, dried under vacuum at RT overnightthen at 70° C. for 3 hr. 0.42 g of white polyethylene is obtained. Theprocess for ethylene polymerization is shown below in exemplary,non-limiting Scheme 10.

The main objective of ethylene polymerization is to verify that thepolymer chain would selectively grow from the core YY structure (i.e.,the derivative of the TVCH linking group) and would not grow from thecapping groups. This is proven by ¹³C NMR analysis (FIG. 8), as no ENBend group is found in the polymer. An ENB group would have two distinctmethyl peaks at ca. 14.0 and 14.5 ppm and four double bond peaks at110-112 ppm and 146-148 ppm. None of these peaks are detected. FIG. 8shows the peaks in the methyl region. The four sharp peaks at 13.7-14.3ppm are the chain end methyl groups. The smaller peak on the left (14.25ppm) is the unlabeled CH₃ group, and the three peaks on the right(13.7-14.2 ppm) are D-labelled CH₂D groups. Apparently, the deuteratedmethanol quench did not result in complete labelling. The broader peaksat 12-13 ppm belong to the CH₃ from the ethyl branches on the core YYstructure (i.e., the derivative of the TVCH linking group). Theintegration of the peaks confirms the presence of roughly equal amountsof Et branches and the chain end methyl groups, i.e., Et:(CH3+CH2D)≈1.This result confirms that polymer quantitatively grows from the core YYstructure (i.e., the derivative of the TVCH linking group) of thedual-headed composition. The absence of methyl peaks at 16 ppm and 19ppm excludes the possibility that the detected Et branches were from adead composition fragment that did not grow polymer.

In addition, the molecular weights of the polymer are measured by GPC,as seen in FIG. 9. The Mn value is reasonably close to the theoreticalMn value of 1900 based on the polymer yield and dosage of dual-headedcomposition, suggesting that the dual-headed composition is fullyutilized for chain transfer reaction. The very narrow molecular weightdistribution also supports that only one type of polymer chains areproduced. The molecular weight distribution would be broader if polymeralso grew from the capping group. Accordingly, the narrow molecularweight distribution further confirms the presence of only one type ofpolymer chain grown from the core YY structure (i.e., the derivative ofthe TVCH linking group).

Furthermore, the one-pot nature of the process of the present disclosureis validated, as the final solution is directly used in subsequentpolymerization without any isolation, purification, or separationrequirements.

WORKING EXAMPLE 2

In a glovebox under nitrogen atmosphere, TVCH (0.47 ml, 2.53 mmol), DEZ(0.1 ml, 0.97 mmol), TEA (1.94 ml, 1.94 mmol) and Co-catalyst A (0.362ml of 0.0644 M solution in methylcyclohexane, 0.023 mmol) are mixed in 6ml of toluene. A sample is taken for ¹H NMR in C6D6, as seen in the“before adding catalyst” spectrum in FIG. 10. Catalyst (A2) (10 mg, 0.02mmol) is dissolved in 1 ml of toluene and added to the mixture toinitiate the reaction to form a first solution. After 1 hr,1,2,4-trivinylcyclohexane is all reacted as evidenced by thedisappearance of vinyl peaks (4.9-5.8 ppm), but some metal-Et remains(ca. 0.3 ppm), as shown in the “1 hr after adding catalyst” spectrum ofFIG. 10. The first solution is brownish and clear, showing no sign ofgel formation. ENB (0.327 g, 2.72 mmol) is added to form a finalsolution containing the composition of Working Example 2. After another1.5 hrs, samples are taken for ¹H NMR showing that metal-Et iscompletely consumed and a small new peak at 5.4ppm attributed to thetri-substituted double bond from ENB, as seen in the “1.5 hrs afteradding ENB” spectrum of FIG. 10. The process of preparing thecomposition of Working Example 2 is illustrated below in exemplary,non-limiting Scheme 11. Accordingly, ¹H NMR analysis shows that thesynthesis reactions proceeded as intended.

Furthermore, an aliquot of the final solution is quenched by water andanalyzed by GCMS (FIG. 11), showing a major group of peaks at m/z=150and a clean single peak at 222, consistent to the expected hydrolyzednorbornyl capping group and the core YY structure (i.e., the derivativeof the TVCH linking group).

WORKING EXAMPLE 3

In a glovebox protected under nitrogen atmosphere, 1,9-decadiene (4.66ml, 25.3 mmol), DEZ (3.0 ml, 29.1 mmol) and Co-catalyst A (1.81 ml, 0.12mmol) are mixed in 80 ml toluene in a 200 ml flask equipped with amagnetic stirbar; catalyst (A2) (47 mg in 10 ml toluene, 0.097 mmol) isadded to initiate the reaction and to form a first solution. After 2 hr,norbornene (1.46 g, 15.5 mmol) is added to the first solution andstirred at RT overnight to form a final solution containing thecomposition of Working Example 3. The process for preparing thecomposition of Working Example 3 (including a hydrolysis step at theend) is illustrated below in exemplary, non-limiting Scheme 12.

A sample of the final solution is hydrolyzed with water/HCl. As seen inFIG. 12, GCMS shows a small peak at m/z=124 corresponding to theexpected capping group in addition to the major peak at m/z=198corresponding to the core YY structure (i.e., the derivative of thedecadiene linking group). Accordingly, GCMS analysis confirms theformation of the intended capped composition.

WORKING EXAMPLE 4

In a glovebox under nitrogen atmosphere, 1,9-decadiene (0.47 ml, 2.53mmol), DEZ (0.1 ml, 0.97 mmol), TEA (1.94 ml, 1.94 mmol) and Co-catalystA (0.362 ml of 0.0644 M solution in methylcyclohexane, 0.023 mmol) aremixed in 6 ml of toluene. A sample is taken for ¹H NMR in C6D6, as seenin the “before adding catalyst” spectrum in FIG. 13. Catalyst (A2) (10mg, 0.02 mmol) is dissolved in 1 ml of toluene and added to the mixtureto initiate the reaction and to form a first solution. After 1 hr,decadiene is all reacted as evidenced by the disappearance of vinylpeaks (4.9-5.8 ppm) with some M-Et remaining (ca. 0.3 ppm), as shown inthe “1 hr after adding catalyst” ¹H NMR spectrum of FIG. 13. The firstsolution is brownish and clear showing no sign of gel formation. ENB(0.327 g, 2.72 mmol) is added to form a final solution containing thecomposition of Working Example 4. After another 1.5 h, samples are takenfor ¹H NMR showing that M-Et is completely consumed, and a small newpeak at 5.4ppm attributed to the trisubstituted double bond from ENB, asseen in the “1.5 hr after adding ENB” spectrum of FIG. 13. The processfor preparing the composition of Working Example 4 is illustrated belowin exemplary, non-limiting Scheme 13.

An aliquot of the final solution is quenched with water and analyzed byGCMS, as seen in FIG. 14. As seen in FIG. 14, GCMS shows a major groupof peaks at m/z=150 and a clean single peak at 198, consistent to theexpected hydrolyzed norbornyl capped group and the core YY structure(i.e., the derivative of the decadiene linking group).

Ethylene Polymerization with the composition of Working Example 4: Tovalidate the composition of Working Example 4, ethylene polymerizationis performed using the composition in a polymerization setup in aglovebox via the reactions illustrated in exemplary, non-limiting Scheme14. ISOPAR™ E(10 ml), and Co-catalyst A (0.0026 mmol) are added to a 40ml glass vial equipped with a stirbar in the drybox. The vial is cappedwith a septum lined lid and connected to an ethylene line via a needle.Another needle is inserted on the lid to let ethylene slowly purge thevial for 2 min. The vial is placed in a heating block at 100° C. Thefinal solution of Working Example 4 (1 ml, 0.3 mmol) and Catalyst (A2)(0.002 mmol) are injected, and the purge needle is removed to maintain atotal pressure at 10 psig. The reaction is maintained for 30 min. Afterpolymerization, 0.5 ml of deuterated methanol (MeOD) is added to quenchthe reaction. The mixture is moved out of the drybox and poured into alarge amount of MeOH. The precipitated polymer is filtered, dried undervacuum at RT overnight then at 70° C. for 3 hr. 0.68 g whitepolyethylene is obtained. Such a procedure is demonstrated below inexemplary, non-limiting Scheme 14.

The main objective of ethylene polymerization is to verify that thepolymer chain would selectively grow from the core YY structure (i.e.,the derivative of the decadiene linking group) and would not grow fromthe capping groups. This is proven by ¹³C NMR analysis (FIG. 15). Asseen in FIG. 15, ¹³C NMR analysis of the polymer shows the ethyl groupsfrom the composition core YY structure as well as the labeled and someunlabelled chain ends due to incomplete quenching. The capping ENBgroups are not detected, indicating that polymer did not grow from thecapping groups. The result confirms the effective and selective transferof polymer chains to the core YY structure of the composition resultingin chain growth in the dual headed fashion.

The GPC curve and molecular weights are shown in FIG. 16. The narrowmolecular weight distribution further confirms the presence of only onetype of polymer chain. A broader MWD would have been obtained had thepolymer chains grew from both the core YY structure and the cappinggroups.

Furthermore, the one-pot nature of the process of the present disclosureis validated, as the final solution is directly used in subsequentpolymerization without any isolation, purification, or separationrequirements.

WORKING EXAMPLE 5

“Composition 1” (an exemplary, non-limiting composition having theformula (I)) is synthesized as follows: In a glovebox under nitrogenatmosphere, TVCH (404 ml, 2.08 mmol), DEZ (20 wt % in toluene, 1.7liter, 2.5 mmol) and Co-catalyst A (0.0699M in methylcyclohexane, 231ml, 16.2 mmol) are added to 2000 ml of toluene in a 6 liter three-neckflask equipped with a mechanic agitator and cooling jacket. Catalyst(A2) (4.1 g in 216 ml toluene, 6.9 mmol) is added over a period of 20minutes to maintain the temperature under 50° C. Samples are takenperiodically for NMR and GCMS to monitor the progress of the reaction.After 6 hours, ENB (112 ml, 0.833 mol) is added and the reaction isstirred overnight. Additional toluene is added to make the total volume5000 ml. The final solution has a zinc concentration of 0.5 M.

The final solution of Composition 1 as prepared above has a light browncolor, which indicates the presence of the catalyst precursor, Catalyst(A2). A small amount of dodecane is added to 20 ml of the final solutionof Composition 1, and a GCMS chromatogram is taken for reference afterhydrolysis, as seen in FIG. 17.

Subsequently, the final solution of Composition 1 is passed through aplug of silica ES757-875; the solution becomes colorless afterfiltration, thereby indicating that the catalyst is removed. A GCMSchromatogram of the filtered final solution is taken after hydrolysis,as seen in FIG. 18. By comparing the GCMS chromatograms of before andafter silica treatment (i.e., by comparing FIGS. 17 and 18), the sameamounts of the capping and core YY structures of Composition 1 are seenrelative to the dodecane peak, thereby indicating no loss of Composition1 by the silica treatment.

Batch Reactor Polymerization with Composition 1: The final solutions ofComposition 1 both before and after silica treatment are tested inethylene-propylene polymerization to confirm the removal of the activecatalyst. The results are shown in Table 1 below. MMAO-3A is added as ascavenger at 7.5 micromol, 100° C., 10 min, and 150 psig.

TABLE 1 Catalyst Composition 1 Silica Mol % Run (A2) (moles) (mmoles)Treatment Ethylene (g) Propylene (g) Yield (g) Mn Mw Mw/Mn C3 1 0.75 0 —25 103 35 161,921 403,560  2.49 — 2 0 3 No 25 103 29 10,758 18,994 1.7716.0 3 0 3 Yes 22 103 Trace — — — — 4 0.75 3 Yes 21 104 15 7,189 17,8242.48 15.0

As seen in Table 1, Run 1 (the control run) is made with Catalyst (A2)but without Composition 1. Run 2 is made Composition 1 without silicatreatment and without additional Catalyst (A2); 29 grams of polymer withlower molecular weight than that of the control run is produced. Run 3is made by the silica treated Composition 1 without additional Catalyst(A2); no polymer is produced, thereby confirming the successful removalof active catalyst from the final solution of Composition 1. Run 4 ismade by the silica treated Composition 1 with additional Catalyst (A2);15 grams of polymer is collected with low molecular weight relative tothe polymer made by the untreated Composition 1, thereby confirming thatthe silica treated Composition 1 is consistent with the behaviorexpected for a chain shuttling agent.

WORKING EXAMPLE 6

“Composition 1” is synthesized as described above in Working Example 5.

“Composition 2” (another exemplary, non-limiting composition having theformula (I)) is synthesized as follows: The same procedure is used asthe synthesis of Composition 1, except that MMAO-3A (“Cocat-2”) is addedin addition to Co-catalyst A (“Cocat-1”). Thus, in the glovebox undernitrogen atmosphere, TVCH (404 ml, 2.08 mmol), MMAO-3A (1.68 M inheptanes, 248 ml, 0.416 mol), DEZ (20 wt % in toluene, 1.7 liter, 2.5mmol) and Co-catalyst A (0.0699M in methylcyclohexane, 231 ml, 16.2mmol) are added to 2000 ml of toluene in a 6 liter three-neck flaskequipped with a mechanic agitator and cooling jacket. Catalyst (A2) (8 gin 336 ml toluene, 13.4 mmol) is added over a period of 20 minutes tomaintain the temperature under 50° C. Samples are taken periodically for¹H NMR and GCMS to monitor the progress of the reaction. After 6 hours,ENB (168 ml, 1.24 mol) is added, and the reaction is stirred overnight.Additional toluene is added to make the total volume 5000 ml. The finalsolution has a zinc concentration of 0.5 M.

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™ E available from ExxonMobil), ethylene,propylene, and molecular weight regulator (hydrogen or chain transferagent) are supplied to a 3.8 L reactor equipped with a jacket fortemperature control. The solvent feed to the reactor is measured by amass-flow controller. A variable speed diaphragm pump controls thesolvent flow rate and pressure to the reactor. At the discharge of thepump, a side stream is taken to provide flush flows for the catalyst,cocatalyst and CSA injection lines. These flows are measured byMicro-Motion mass flow meters and controlled by control valves. Theremaining solvent is combined with ethylene, propylene and hydrogen andfed to the reactor. The temperature of the solvent/monomer solution iscontrolled by use of a heat exchanger before entering the reactor. Thisstream enters the bottom of the reactor. The catalyst componentsolutions are metered using pumps and mass flow meters and are combinedwith the catalyst flush solvent and introduced into the bottom of thereactor. The reactor is liquid full at 500 psig with vigorous stirring.Product is removed through exit lines at the top of the reactor. Allexit lines from the reactor are steam traced and insulated.Polymerization is stopped by the addition of a small amount of waterinto the exit line along with any stabilizers or other additives andpassing the mixture through a static mixer. The product stream is thenheated by passing through a heat exchanger before devolatilization. Thepolymer product is recovered by extrusion using a devolatilizingextruder and water cooled pelletizer. The process conditions and resultsare listed in Tables 2 and 3. Selected polymer properties are providedin Table 4. A ¹³C NMR spectrum of a selected product is shown in FIG.19. The TGIC curves of selected products are shown in FIG. 20.

TABLE 2 Reactor Control Catalyst MW Solvent, C2 Production Temperature,concentration, Run regulator lbs/hr C2, lbs/hr C3, kg/hr H2, sccmconversion, % rate, lbs/hr C. ppm 1 H2 51.68 4.13 2.18 1599 91.4 3.77102.2 60.8 2 H2 50.4 4.12 1.69 719 90.7 3.74 103.3 60.8 3 H2 48.8 4.131.3 184 89.9 3.72 109.9 60.8 4 H2 49.6 4.13 1.17 199 91.5 3.78 109.760.8 5 DEZ 50.9 4.12 2.11 0.43 90.5 3.81 103.6 60.8 6 DEZ 52.05 4.112.63 0.40 91 3.85 102.3 60.8 7 Comp. 2 52.94 4.13 2.87 0.49 89.5 4.84101.2 60.8 8 Comp. 2 54.11 4.12 4.31 0.56 89.40 6.27 105.1 60.8 9 Comp.2 55.34 4.12 4.95 0.45 89.6 6.88 105.0 60.8 10 Comp. 1 43.34 3.09 4.650.45 90.6 6.12 114.9 60.8 11 Comp. 1 41.18 3.48 2.40 0.45 92.6 4.31105.0 60.8 12 Comp. 1 41.25 3.47 3.20 0.47 90.2 5.05 105.3 60.8

TABLE 3 Cocat-1 Cocat-2 Comp. ½ Catalyst concentration, Cocat-1concentration, Cocat-2 concentration, Comp. ½ Catalyst eff. Run flow,lbs/hr ppm flow, lbs/hr ppm flow, lbs/hr ppm flow, lbs/hr MM-lb/lb 10.199 215.0 0.450 20.0 0.460 0.31 2 0.189 215.0 0.429 20.0 0.430 0.32 30.164 215.0 0.373 20.0 0.379 0.37 4 0.153 215.0 0.347 20.0 0.350 0.41 50.219 215.0 0.496 99.6 0.204 32699 0.397 0.29 6 0.258 461.0 0.271 99.60.238 32699 0.463 0.25 7 0.431 461.0 0.453 99.6 0.395 32699 0.649 0.19 80.348 461.0 0.371 99.6 0.318 32699 0.740 0.30 9 0.509 461.0 0.543 99.60.467 32699 1.000 0.22 10 0.609 461.0 0.644 99.6 0.550 32699 0.688 0.1711 0.535 461.0 0.568 99.6 0.490 32699 0.693 0.13 12 0.469 461.0 0.50199.6 0.430 32699 0.693 0.18

TABLE 4 Product Melt Brookfield Zn in MW Density Mooney, Index,Viscosity, polymer, Run regulator [g/cc] MU I2 cP ppm Mn Mw Mw/Mn Tm, C.Tc, C. Hf, J/g P wt % 1 H2 0.909 16346 8,534 20,910 2.45 94.0, 81.2 79.4112.4 2 H2 0.912 17.3 379359 20,834 51,178 2.46 100.3 85.5 106.3 3 H20.911 37.45 55,508 143,374 2.58 104.6 92.9 104.6 4 H2 0.914 49.2 62,884166,923 2.65 106.8 95.3 106.4 5 DEZ 0.916 76750 13,085 27,646 2.11 98.9,87.8 85.4 114.1 11.5 6 DEZ 0.909 24943 2710 10,323 20,696 2.00 96.2,84.2 82.8 111.8 12.5 7 Comp. 2 0.915 40.7 4670 16,482 38,652 2.35  94.880.5 96.2 12.9 8 Comp. 2 0.906 190631 4900 14,567 34,533 2.37  83.2 68.980.4 17.1 9 Comp. 2 0.906 95102 7060 10,433 24,469 2.35  80.2 67.6 83.118.2 10 Comp. 1 0.890 64402 5830 11,170 26,171 2.34 64.1, 44.1 55.1 63.922.8 11 Comp. 1 0.890 30404 5610 10,351 23,172 2.24   65, 44.6 57.8 6623.2 12 Comp. 1 0.911 65703 5367 12,742 29,065 2.28 85.7, 74.0 70.9 88.116.9

As seen in Table 3, the results showed that the Compositions 1 and 2 ofWorking Example 6 are effective chain transfer agents to produce polymerwith desired the molecular weights. The ¹³C NMR analysis confirmed thepresence of core YY group (i.e., the derivative of a linking group) inthe polymer. The ratio of the chain end methyl groups to the ethylgroups from the core structure is approximately one, suggesting thatthere is one “core” structure fragment in each polymer chain.

Furthermore, the one-pot nature of the process of the present disclosureis validated, as the final solution is directly used in subsequentpolymerization without any isolation, purification, or separationrequirements.

What is claimed is:
 1. A composition having the formula (I):

wherein: each MA is Al, B, or Ga; each MB is Zn or Mg; m is number from0 to 1; n is a number from 1 to 100; YY is a derivative of a linkinggroup, wherein the linking group is a C₄₋₁₀₀ hydrocarbon comprising atleast two vinyl groups and optionally includes at least one heteroatom;and each J2 and J3 is a derivative of a strained olefin.
 2. Thecomposition of claim 1 having the following structural formulae:

or

wherein J1 is hydrogen or a C₁₋₂₀ alkyl group.
 3. The composition ofclaim 1, wherein each J2 and J3 is selected from the group consisting ofthe following structural formulae:

, and, wherein: J1 is hydrogen or a C₁₋₂₀ alkyl group; and each XX2,XX3, XX4, and XX5 is hydrogen, a substituted or unsubstituted C₁₋₂₀alkyl group, or a substituted or unsubstituted C₆₋₂₀ aryl group, whereinXX2, XX3, XX4, and XX5 may be the same or different, wherein each XX2,XX3, XX4, and XX5 optionally includes at least one heteroatom, andwherein two of XX2, XX3, XX4, and XX5 may optionally form cyclicstructures.
 4. The composition of claim 1, wherein each J2 and J3 isselected from the group consisting of the following structural formulae:

, and wherein J1 is hydrogen or a C₁₋₂₀ alkyl group.
 5. The compositionof claim 1 having the following structural formula:

wherein: J1 is hydrogen or a C₁₋₂₀ alkyl group; and ZZ is a linear orbranched C₄₋₁₀₀ hydrocarbyl group that optionally includes at least oneheteroatom, and wherein ZZ may be aliphatic or aromatic.
 6. Thecomposition of claim 5, wherein YY is a derivative of an alpha,omega-diene.
 7. The composition of claim 5, wherein each J2 and J3 isselected from the group consisting of the following structural formulae:

, and, wherein: J1 is hydrogen or a C₁₋₂₀ alkyl group; and each XX2,XX3, XX4, and XX5 is hydrogen, a substituted or unsubstituted C₁₋₂₀alkyl group, or a substituted or unsubstituted C₆₋₂₀ aryl group, whereinXX2, XX3, XX4, and XX5 may be the same or different, wherein each XX2,XX3, XX4, and XX5 optionally includes at least one heteroatom, andwherein two of XX2, XX3, XX4, and XX5 may optionally form cyclicstructures.
 8. The composition of claim 5, wherein each J2 and J3 isselected from the group consisting of the following structural formulae:

, and, wherein J1 is hydrogen or a C₁₋₂₀ alkyl group.
 9. A process forpreparing the composition having the formula (I):

wherein: each MA is Al, B, or Ga; each MB is Zn or Mg; m is number from0 to 1; n is a number from 1 to 100; YY is a derivative of a linkinggroup, wherein the linking group is a C₄₋₁₀₀ hydrocarbon comprising atleast two vinyl groups and optionally includes at least one heteroatom;and each J2 and J3 is a derivative of a strained olefin, the processcomprising: (a) combining a linking group, an organometallic compound, aco-catalyst, a solvent, a first catalyst precursor, and a strainedolefin, and (b) obtaining a final solution comprising the compositionhaving the formula (I), wherein the linking group is a C₄₋₁₀₀hydrocarbon comprising at least two vinyl groups and optionally includesat least one heteroatom.
 10. The process of claim 9, wherein the linkinggroup is 1,2,4trivinylcyclohexane and the strained olefin is selectedfrom the group consisting of the following structural formulae:

, and, wherein: each XX2, XX3, XX4, and XX5 is hydrogen, a substitutedor unsubstituted C₁₋₂₀ alkyl group, or a substituted or unsubstitutedC₆₋₂₀ aryl group, wherein XX2, XX3, XX4, and XX5 may be the same ordifferent, wherein each XX2, XX3, XX4, and XX5 optionally includes atleast one heteroatom, and wherein two of XX2, XX3, XX4, and XX5 mayoptionally form cyclic structures.
 11. The process of claim 9, whereinthe strained olefin is selected from the group consisting of thefollowing structural formulae:


12. The process of claim 9, wherein the linking group is analpha,omega-diene and the strained olefin is selected from the groupconsisting of:

, and, wherein: each XX2, XX3, XX4, and XX5is hydrogen, a substituted orunsubstituted C₁₋₂₀ alkyl group, or a substituted or unsubstituted C₆₋₂₀aryl group, wherein XX2, XX3, XX4, and XX5 may be the same or different,wherein each XX2, XX3, XX4, and XX5 optionally includes at least oneheteroatom, and wherein two of XX2, XX3, XX4, and XX5 may optionallyform cyclic structures.
 13. The process of claim 12, wherein thestrained olefin is selected from the group consisting of:


14. The process of claim 9, wherein the organometallic compoundcomprises a trivalent metal, a divalent metal, or a mixture of atrivalent metal and a divalent metal.
 15. A polymerization process forpreparing a polymer composition, the process comprising: contacting atleast one olefin monomer with a catalyst composition; wherein thecatalyst composition comprises the reaction product of a second catalystprecursor, a co-catalyst, and the composition of claim
 1. 16. Apolymerization process for preparing a polymer composition, the processcomprising: contacting at least one olefin monomer with a catalystcomposition; wherein the catalyst composition comprises the reactionproduct of a second catalyst precursor, a co-catalyst, and thecomposition prepared according to the process of claim
 9. 17. Apolymerization process for preparing a polymer composition, the processcomprising: contacting at least one olefin monomer with a catalystcomposition; wherein the catalyst composition comprises the reactionproduct of a second catalyst precursor, a co-catalyst, and thecomposition prepared by the process of claim 9, and wherein the secondcatalyst precursor is the same compound as the first catalyst precursor.18. A polymer composition obtained by the process of claim
 15. 19. Acatalyst composition comprising the reaction product of at least onecatalyst precursor, at least one co-catalyst, and the composition ofclaim
 1. 20. A process for preparing a telechelic functional polymercomprising performing functional group conversion reactions atcarbon-metal bonds of the composition of claim 1.